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CN101421641A - Films for optical use and methods of making such films - Google Patents

Films for optical use and methods of making such films Download PDF

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Publication number
CN101421641A
CN101421641A CNA2005800088685A CN200580008868A CN101421641A CN 101421641 A CN101421641 A CN 101421641A CN A2005800088685 A CNA2005800088685 A CN A2005800088685A CN 200580008868 A CN200580008868 A CN 200580008868A CN 101421641 A CN101421641 A CN 101421641A
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China
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goods
layer
substrate
material layer
optical
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Chinese (zh)
Inventor
安格尔·N·尼古洛夫
简·J·王
欧阳旭
冯柳
邓将东
邓学工
格雷格·E·布朗德
龙尼·P·瓦格斯
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Nanoopto Corp
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Nanoopto Corp
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Abstract

Films for optical use, articles containing such films, methods for making such films, and systems that utilize such films, are disclosed.

Description

Film for optical use and the method for making this film
Technical field
The present invention relates to a kind of film for optical use, comprise this film goods, make the method for this film and use the system of this film.
Background technology
Generally can use optical device and optical system in the time of need handling light.The example of optical device comprises lens, polarizer, optical filtering, antireflection film, delayer (for example, quarter-wave plate), and beam splitter (for example, polarization beam apparatus and unpolarized beam splitter).
Summary of the invention
The present invention relates to film for optical use, comprise this film goods, make the method for this film and use the system of this film.
On the one hand, the present invention provide a kind of on substrate film forming method, this method comprises: form first material layer by a plurality of first single layer of material of sequential aggradation, one of this first single layer of material is deposited on the first surface of substrate, wherein, this film comprises polymkeric substance at the bottom of comprising first material layer and this title.
On the other hand, the present invention provides a kind of method that forms multilayer film on optical module, this method comprises: the individual layer by a plurality of first materials of sequential aggradation is to form first material layer, and one of individual layer of this first material is deposited on the first surface of optical module; And the individual layer by a plurality of second materials of sequential aggradation to be to form second material layer, and one of individual layer of this second material is deposited on the surface of first material layer, and wherein multilayer film comprise this first material layer and this second material layer, and optical module is lens.
On the other hand, the present invention provides a kind of method, comprising: the method for using ald is simultaneously at the first and second surface deposition films of substrate, and this first surface is opposite with this second surface.
On the other hand, the present invention provides a kind of method, comprising: the method for using ald is simultaneously at the first and second surface deposition films of optical substrate, and this first surface is opposite with this second surface.
On the other hand, the present invention provides a kind of method, comprising: the method deposit multilayer film on the surface of the substrate that comprises polymkeric substance that uses ald.
On the other hand, the present invention provide a kind of on substrate film forming method, comprise: the individual layer by a plurality of first materials of sequential aggradation forms first material layer, one of individual layer of this first material is deposited on the first surface of substrate, wherein, film comprises this first material layer, and substrate comprises lens.
On the other hand, the present invention provides and is a kind ofly comprising film forming method on the substrate of curved surface, comprise: the individual layer by a plurality of first materials of sequential aggradation is to form first material layer, one of individual layer of this first material is deposited on the curved surface of substrate, and wherein film comprises this first material layer.
On the other hand, the present invention provide a kind of on substrate film forming method, comprise: the individual layer by a plurality of first materials of sequential aggradation is to form first material layer, one of the individual layer of this first material sequential aggradation is on the first surface and second surface of substrate, wherein film comprises this first material layer, and first surface is opposite with second surface.
On the other hand, the present invention provide a kind of on substrate film forming method, comprise: the individual layer by a plurality of first materials of sequential aggradation is to form first material layer, one of individual layer of this first material is deposited on the non-coplanar first surface and second surface of substrate, wherein film comprises this first material layer, and first surface links to each other with second surface.
On the other hand, the present invention provides a kind of method, comprising: the method deposit multilayer film on the surface of lens that uses ald.
On the other hand, the present invention provides a kind of method, comprising: the method deposit multilayer film on curved surface or patterned surface that uses ald.
Embodiment can comprise one or more following features.
The individual layer that deposits a plurality of first materials can comprise: the individual layer of precursors to deposit and the individual layer of precursor is exposed in the reactant, and to form the individual layer of first material.This reactant can with this precursor generation chemical reaction to form first material.For example, this reactant can this precursor of oxidation to form first material.The individual layer that deposits this precursor can comprise introduces first gas that comprises this precursor in the reaction chamber of accommodating substrates.The pressure of this first gas can be about 0.01Torr to about 100Torr in the reaction chamber.The individual layer of this precursor is exposed to reactant can be comprised to reaction chamber and introduce second gas that comprises reactant.The pressure of this second gas can be about 0.01Torr to about 100Torr in the reaction chamber.After first gas is introduced and before the introducing of second gas, can introduce the 3rd gas to reaction chamber.The 3rd gas can be inertia for this precursor.The 3rd gas can comprise at least a gas that can select from helium, argon, nitrogen, neon, krypton and xenon.This precursor can be from three (tert-butyl group) silanol, (CH 3) 3Al, TiCl 4, SiCl 4, SiH 2Cl 2, TaCl 3, AlCl 3, ethoxy hafnium and ethoxy thallium, middle selection.This first material can be dielectric material.
This method can comprise: the individual layer by a plurality of second materials of sequential aggradation is to form second material layer, and one of individual layer of this second material layer is deposited on first material layer, and wherein this second material is different from this first material, and film comprises this second material layer.Depositing a plurality of second single layer of material can comprise: the individual layer of precursors to deposit and the individual layer of this precursor is exposed in the reactant to form the individual layer of second material.This reactant can with this precursor generation chemical reaction to form second material.For example, this reactant can this precursor of oxidation to form second material.The individual layer that deposits this precursor can comprise introduces first gas that comprises this precursor in the reaction chamber of accommodating substrates.The pressure of this first gas can be about 0.01Torr to about 100Torr in the reaction chamber.The individual layer of this precursor is exposed to reactant to be comprised to reaction chamber and introduces second gas that comprises reactant.The pressure of this second gas is that about 0.01Torr is to about 100Torr in the reaction chamber.After first gas is introduced and before the introducing of second gas, reaction chamber can be cleaned gas purification.This Purge gas for first precursor can be for inertia.This Purge gas can comprise at least a gas of selecting from helium, argon, nitrogen, neon, krypton and xenon.This precursor can be from three (tert-butyl group) silanol, (CH 3) 3Al, TiCl 4, SiCl 4, SiH 2Cl 2, TaCl 3, AlCl 3, ethoxy hafnium and ethoxy thallium, middle selection.This second material can be dielectric material.
This method can also comprise: form the 3rd material layer on the surface of second material layer, wherein, the 3rd material is different from second material, and film comprises the 3rd material layer.The 3rd material can be identical with first material.Can use the method for ald to deposit the 3rd material layer.This method also can comprise: form the 4th material layer on the surface of the 3rd material layer, wherein, the 4th material is different from the 3rd material and film comprises the 4th material layer.The 4th material can be identical with second material.Can use the method for ald to deposit the 4th material layer.This method can comprise the extra play that formation is supported by the 4th material layer.Can use the method for ald to form extra play.
Substrate can be optical module.This method can comprise: form first material layer on the second surface of substrate, simultaneously, form first material layer on first surface, wherein, this second surface is opposite with this first surface or continuous.Individual layer that can be by a plurality of first materials of sequential aggradation is to form first material layer at second surface, one of individual layer of this first material layer is deposited on the second surface of substrate.
This method can comprise: being deposited on formation second material layer on first material layer of substrate second surface, simultaneously, form second material layer on first material layer on the first surface, wherein, this second surface is opposite with this first surface or continuous.Can form second material layer on first material layer by the individual layer of a plurality of second materials of sequential aggradation, one of individual layer of this second material is deposited on the surface that is deposited on first material layer on the second surface.
When forming first material layer, underlayer temperature be about 500 ℃ or lower (for example, about 300 ℃ or lower, about 200 ℃ or lower, about 150 ℃ or lower, about 100 ℃ or lower, about 80 ℃ or lower, about 70 ℃ or lower, about 60 ℃ or lower, about 50 ℃ or lower).
Comprise among the embodiment of polymkeric substance at substrate, polymkeric substance can be thermosetting polymer or thermoplastic polymer.
In aspect another, the present invention provides a kind of goods, and these goods comprise: substrate, and it has first surface and the second surface that links to each other with this first surface, and this first and second surface is non-coplanar; Be arranged at first multilayer film on the first surface, be arranged at second multilayer film on the second surface, wherein, second multilayer film link to each other with first multilayer film.
On the other hand, the present invention provides a kind of goods, comprises optical module, its have first surface and with this first surface opposed second surface; Be arranged at first material layer and first material layer that is arranged on the second surface on the first surface, wherein, the vertical optical thickness of first material layer of a certain position on the first surface the vertical optical thickness of first material layer of the corresponding position on the second surface about 5% in.
On the other hand, the present invention provides a kind of goods, comprises substrate, and it has a radius-of-curvature and is about 10 meters or littler surface, and wherein, this surface has first and second positions, and the angle between the surface normal of this first and second position is about 2 degree or littler; Be deposited on lip-deep film, wherein this film comprises first material layer, this layer the vertical optical thickness of primary importance be this layer the vertical optical thickness of the second place about 1% within.
On the other hand, the present invention provides a kind of goods, comprises substrate, its have first surface and with the first surface opposed second surface; Be deposited on the first film on the first surface; With second film that is deposited on the second surface, wherein, the vertical optical thickness of the first film in the primary importance place on the first surface the vertical optical thickness of second film of the corresponding position on the second surface about 5% in.
On the other hand, the present invention provides a kind of goods, comprising: comprise the substrate of polymkeric substance and be arranged at multilayer film on the first surface of substrate.
On the other hand, the present invention provides a kind of optical filtering, comprising: limit the multilayer film of optical axis, wherein the wavelength of propagating along optical axis of optical filtering transmission 50% is λ 1Light, and optical filtering transmission 50% become 30 wavelength that are incident on the multilayer film of degree angles with optical axis be λ 2Light, wherein, | λ 1-λ 2| be about 30nm or still less.
Embodiment can comprise one or more following features.
First multilayer film and second multilayer film can comprise the successive layers of first material.First multilayer film and second multilayer film comprise the successive layers of second material, and wherein, second material is different from first material, and the first material successive layers supports the second material successive layers.First multilayer film and second multilayer film can comprise 3 or more successive layerss, and wherein, adjacent layer is formed by different materials.
Substrate can be optical module (for example, lens, as Fresnel lens, optical flat).Substrate can comprise glass.Glass can be from optical glass, glass ceramics, and quartz is selected in silica glass and the soda-lime glass.Perhaps, or additionally, substrate can comprise polymkeric substance (for example, thermosetting polymer or thermoplastic polymer).Polymkeric substance is from polysilicates, acrylic, and polyester, tygon, polypropylene is selected in Polyvinylchloride and the poly-methyl acrylic methyl esters.Substrate comprise glass transition temperature be about 250 ℃ or lower material (for example, about 200 ℃ or lower, about 150 ℃ or lower, about 100 ℃ or lower, about 80 ℃ or lower).Substrate can be included in 10% the backing material that thermal expansivity between 0 ℃ to 300 ℃ is the first material coefficient of thermal expansion coefficient.The surface can have about 100 meters or littler radius-of-curvature.Perhaps the surface can be roughly the plane.The surface can be patterned surface.First material can be dielectric material.First material can be oxide.For example, oxide can be metal oxide.In certain embodiments, metal oxide can be from SiO 2, Al 2O 3, Nb 2O 5, TiO 2, ZrO 2, HfO 2, and Ta 2O 5The middle selection.
Successive layers can have and is about 1nm or bigger vertical optical thickness (for example, be about 10nm or bigger, be about 20nm or bigger).In certain embodiments, successive layers has and is about 5000nm or littler vertical optical thickness (for example, be about 1000nm or littler, be about 500nm or littler).
First multilayer film and second multilayer film are antireflection film.In certain embodiments, these goods are optical filtering.This optical filtering can be infrared filter.This infrared filter reduces the optical transmission rate of wavelength from about 650nm to about 1100nm by these goods.Optical filtering can be the ultraviolet filter.The ultraviolet filter can reduce wavelength by these goods less than the optical transmission rate of 400nm.
The refractive index of first material can be different from the refractive index of second material.The vertical optical thickness of the successive layers of first material can be identical with the vertical optical thickness of the successive layers of second material.Perhaps, the vertical optical thickness of the successive layers of first material can be different from the vertical optical thickness of the successive layers of second material.These goods can comprise the 3rd lip-deep the 3rd multilayer film that are arranged at substrate, and the 3rd surface is opposite with first surface.This first, the second, be identical with the 3rd multilayer film.
In certain embodiments, λ 1Be about 650nm.
In aspect another, the present invention provides a kind of optical system, comprising: be used for and will arrive the lens on picture plane from the photoimaging of object; And optical filtering, this optical filtering comprises a plurality of layers of relative lens position, in order to make wavelength with respect to the identical optical system that does not have optical filtering is that the light of λ reduces about 20% or more in the amount of being assembled as plane place, and one of wherein said a plurality of layers are deposited on the first surface of lens.
On the other hand, the present invention provides a kind of optical system, comprise: with respect to the optical filtering of lens and the setting of picture plane, wherein, optical filtering comprises the substrate with first surface and second surface, wherein this first surface is opposite with this second surface, and first multilayer film and second multilayer film are arranged at respectively on this first surface and this second surface, and wherein first multilayer film are identical with second multilayer film.
On the other hand, the present invention provides a kind of digital camera that comprises one of above optical system.
In aspect another, the present invention provides a kind of mobile phone that comprises above digital camera.
Embodiment can comprise one or more following features.
First surface can have and is about 2 meters or littler radius-of-curvature.Can be about 5cm or nearlyer (for example, be about 1cm or nearer, be about 0.5cm or nearer) apart from lens as the plane.Optical system can comprise the detector that is positioned place, picture plane.Detector can be charge-coupled device (CCD) array or complementary metal oxide semiconductor (CMOS) (CMOS) array.Optical filtering can be arranged on the surface of detector.
Described a plurality of layer comprises a plurality of dielectric layers.This alternating layer of a plurality of layers has different refractivity.These a plurality of layers comprise the layer on the second surface that is arranged at the lens opposite with first surface.λ can be about 650nm or bigger.For example, λ can be between about 650nm and 1100nm.It is that the light of λ reduces about 50% or more (for example, about 80% or more, about 90% or more, about 95% or more) that optical filtering can make the wavelength that focuses on as the plane.
Above-mentioned optical system can comprise from the photoimaging of object second lens to the picture plane.One of a plurality of layers of optical filtering can be set on the surface of second lens.Imaging light has at the first surface place and is about 20 degree or littler maximum divergence (for example, about 15 degree or littler, about 10 degree or littler).Optical filtering can be set between lens and the picture plane.
Embodiments of the invention can comprise one or more following advantages.
In certain embodiments, film comprises one or more height layer (for example, the thickness height is even, and the refractive index height is even) uniformly, and it causes, for example, film itself highly evenly (for example, the thickness height is even, and the refractive index height is even).A kind of goods, optical device for example is owing to comprise that one or more this films can represent higher performance.For example, the optical filtering that comprises one or more this films can stop unwanted wavelength and the wavelength of transmission needs efficiently simultaneously efficiently.
But layer one deck connects one deck ground repeated deposition highly uniformly, and (for example, the thickness height is even so that highly uniform multilayer film to be provided, the refractive index height is even), and on different substrates, provide have the height conforming layer (for example, the thickness height is even, and the refractive index height is even) film.The goods such as optical device that comprise this film can be manufactured into the uniformity coefficient specification that meets strictness.For example, the optical filtering that comprises this film can be worked under the optical property specification requirement of strictness.For example, the position of the passband edge of a collection of optical filtering with this film can be basic identical each other.
In certain embodiments, film can comprise one or more conformal layers by substrate supports (conformal layer).This conformal layer also can be (for example, the thickness height is even, and the refractive index height is even) highly uniformly.The goods such as optical device that comprise one or more this optical thin films can represent higher performance.For example, the patterned surface of Fresnel lens can be coated with antireflection (AR) film, thinks that lens provide higher performance." ghost image " that the reflection of not expecting that takes place on the AR film on this lens can reduce owing to the patterned surface at lens occurs.Another example and for example, high homogeneous film (for example, the thickness height is even, and the refractive index height is even) can be deposited on the curved surface, for example is deposited on the inside surface of the surface of globe lens or integrating sphere.
In certain embodiments, said method allows a plurality of (for example, opposite) surperficial sequential aggradation of substrate.Can reduce the cost and the complexity of deposit film like this.This method also can allow a plurality of essentially identical films to be formed on the different surfaces of substrate, and with the minimizing sedimentation time, and/or minimizing is to the extra process of film.Make the goods of making in this way such as optical device, can reach strict optical specification.For example, in single deposition cycle, the AR film can be covered to a plurality of surfaces of substrate (for example, lens, prism, or optical flat).
In some specific embodiment, said method can be used for partly or entirely coating substrate.For example, when the substrate that needs protection is avoided environmental impact (for example, when substrate being exposed to the performance parameter that can destroy substrate in the environment), this encapsulation is favourable.
In certain embodiments, said method be subjected to heat-labile substrate (for example, glass transition temperature is about 300 ° or lower polymer substrate) compatible mutually.
In some specific embodiment, can use said method to make integrated optics assembly (for example, as the lens of the substrate of one or more films, described film is for example for forming the film of optical filtering simultaneously).This integrated package can be used for reducing the number that appears to the dispersion assembly in the optical system of certain specific purpose design.Can for example reduce volume like this, reduce cost and/or the complexity of optical system.
Other features and advantages of the present invention will be by instructions, accompanying drawing and claims and obvious.
Description of drawings
Figure 1A is the sectional view of optical filtering.
Figure 1B is the sectional view of the part of optical filtering shown in Figure 1A.
Fig. 1 C illustrates a last incident and optical filtering transmitted light spectrogram from the transmission situation of axle incident.
Fig. 2 A is the synoptic diagram of atomic layer deposition system.
Fig. 2 B is the process flow diagram of atom layer deposition process.
Fig. 3 is the sectional view of the continuous multilayer film that deposit on the continuous surface of substrate.
Fig. 4 is the sectional view that has the lens of film on opposed surface.
Fig. 5 is the partial cross section figure that has the Fresnel lens of a film on patterned surface.
Fig. 6 is the synoptic diagram that comprises the imaging system of optical filtering.
Fig. 7 comprises the synoptic diagram of the imaging system of optical filtering for another.
Fig. 8 comprises the synoptic diagram of the imaging system of optical filtering for another.
Fig. 9 comprises the synoptic diagram of the imaging system of optical filtering for another.
Figure 10 is an optical filtering at the transmitted spectrum of light during with 0 ° and 30 ° of incidents.
Figure 11 is another optical filtering at the transmitted spectrum of light during with 0 ° of incident.
The identical representative similar elements that meets in each figure.
Embodiment
With reference to Figure 1A, optical filtering 10 is made of two multilayer film 11 and 12, is arranged on the opposite surfaces 21 and 22 of substrate 20 (for example, glass optical flat).Optical filtering 10 reflects the light of some wavelength that drops on the filter and propagate along axle 50 fully, and the abundant light of other wavelength of transmission.Optical filtering 10 also reflect drop on the filter and with the light of axle 50 some wavelength at angle, and the light of other wavelength of transmission.Multilayer film 11 and 12 all comprise high reflectance that replaces and the antiradar reflectivity layer that the formation of some is formed by dielectric material.
The structure of multilayer film 11 is shown in Figure 1B.Multilayer film 11 comprise 7 high refractive index layer 30 and 7 antiradar reflectivity layers 32.The The Nomenclature Composition and Structure of Complexes of multilayer film 12 is the same with the The Nomenclature Composition and Structure of Complexes of film 11 repeatedly.In other words, two multilayer film all comprise the dielectric layer of equal number, and the composition of equivalent layer is also identical with thickness in the film.Here, equivalent layer refers to be in the multilayer film 11 and 12 layer of identical relative position in multilayer film.
Thickness of each layer in the multilayer film 11 and 12 and composition depend on the desired light spectral property of optical filtering 10.In some cases, the thickness of each layer is about 0.25 λ/n, and wherein λ is the wavelength of the required reflection of filter, and n is the reflectivity of this layer.Certainly, the thickness of known layer can change according to the reflectivity of the employed material of cambium layer.
In certain embodiments, the thickness of each layer can be determined by the algorithm according to the thickness of the optical characteristics Optimization Layer of required optical filtering.For example, if wish to obtain maximum reflectivity on the spectrum specific part, algorithm can determine to have the reflectivity of the filter of different layer thickness combination, to obtain the highest structure of reflectivity.The business software that is used for carrying out this calculating is exemplified as the FilmWizard in Scientific ComputingInternational company (California, USA Carlsbad city) TMAnd the TFCalc of SoftwareSpectra company (Ore. Portland city).
Here, the vertical thickness of Ceng a part refers to along the thickness of this part of this layer of the normal direction of the substrate surface of adjacent this this part of layer part.Generally, by utilizing electron microscope method, ellipsometry is studied the cross section of this layer or by making computational data and spectroscopic data parameter matching can determine the thickness (for example, perpendicular layers thickness) of layer.
Here, the vertical optical thickness of Ceng a part refers to the thickness of this part of this layer on the normal direction of the most contiguous with it substrate surface part.
Here, the optical thickness of Ceng a part refers to the product of the refractive index of the thickness of this part of this layer and this part.When this part of this layer is optics when uneven (for example, changing in layer along the direction refractive index of thickness measure), the refractive index of optical thickness for obtaining with respect to the thickness product branch.For optically homogeneous layer, this integrated value is classified as aforementioned definitions.
In each layer of multilayer film, the vertical optical thickness of each layer can be identical or different with the vertical optical thickness of other layer.For example, (for example, about 10nm among) the embodiment, the vertical optical thickness of each layer can be 0.25 λ to be designed to reflect narrowband wavelength at optical filtering 10 0, λ wherein 0Be the centre wavelength in the zone of reflections.Alternatively, when optical filtering 10 is designed to reflect broad band wavelength (for example, about 100nm or more, about 150nm or more, about 200nm or more), the vertical optical thickness of layer can change.In this example, for the different wave length λ in the expectation zone of reflections i, not on the same group the layer of each multilayer film can have and equals 0.25 λ iVertical optical thickness.In certain embodiments, the vertical optical thickness of each layer can be at about 20nm to the scope of about 1000nm.For example, every layer vertical optical thickness can be about 50nm or more (for example, about 100nm or more, about 150nm or more, about 200nm or more, about 250nm or more, about 300nm or more).In an embodiment, the vertical optical thickness of this layer can be about 800nm or littler (for example, about 600nm or littler, about 500nm or littler).
Usually, the vertical thickness of each layer in the multilayer film can be uniform substantially.For example, the vertical thickness of one known layer can change about 2% or still less (for example between the different parts of one deck, about 1% or still less, about 0.5% or still less, about 0.2% or still less, about 0.1% or still less, about 0.05% or still less, about 0.02% or still less, about 0.01% or still less, 0.001% or still less).In certain embodiments, between the different parts of vertical thickness at one deck of each layer of multilayer film, can change about 10nm or (for example, about 8nm or still less still less, about 5nm or still less, about 3nm or still less, about 2nm or still less, about 1nm or still less, about 0.5nm or still less).
Generally, the vertical optical thickness of multilayer film 11 and each layer of 12 can be uniform substantially.In certain embodiments, the vertical optical thickness of one deck can change about 2% or still less (for example between the different parts of one deck, about 1% or still less, about 0.5% or still less, about 0.2% or still less, about 0.1% or still less, about 0.05% or still less, about 0.02% or still less, about 0.01% or still less, 0.001% or still less).The vertical optical thickness of one or more sedimentary deposits can change about 20nm or still less (for example, about 10nm or still less, about 5nm or still less, about 3nm or still less, about 2nm or still less, about 1nm or still less, about 0.5nm or still less) between the different parts of one deck.
As previously mentioned, thickness and the component in multilayer film 11 and 12 the equivalent layer is basic identical.For example, those layers of next-door neighbour's substrate surface are equivalent layer in each multilayer film.In certain embodiments, the perpendicular layers thickness of equivalent layer in the relevant position of each multilayer film (for example, the position of optical axis 50 cross-section each multilayer film) can change about 2% or still less (for example, about 1% or still less, about 0.5% or still less, about 0.2% or still less, about 0.1% or still less, about 0.05% or still less, about 0.02% or still less, about 0.01% or still less, 0.001% or still less).In certain embodiments, the vertical thickness of one or more equivalent layers can change about 10nm or (for example, about 8nm or still less still less in the relevant position of multilayer film 11 and multilayer film 12, about 5nm or still less, about 3nm or still less, about 2nm or still less, about 1nm or still less, about 0.5nm or still less).
In addition, the vertical optical thickness of equivalent layer can be uniform substantially in multilayer film 11 and the multilayer film 12.In certain embodiments, the vertical optical thickness of multilayer film equivalent layer can have between equivalent layer, have about 2% or variation still less (for example, about 1% or still less, about 0.5% or still less, about 0.2% or still less, about 0.1% or still less, about 0.05% or still less, about 0.02% or still less, about 0.01% or still less, 0.001% or still less).The vertical optical thickness of equivalent layer can change about 15nm or still less (for example, about 10nm or still less, about 5nm or still less in the corresponding position of multilayer film 11 and multilayer film 12, about 3nm or still less, about 2nm or still less, about 1nm or still less, about 0.5nm or still less).
In order to the dielectric material of the layer that forms multilayer film 11 and 12 (for example according to its optical characteristics, they play the refractive index of length at film, with absorption spectrum) at these wavelength, its to each other and and substrate between compatibility, with and select with compatibility in order to the technological process of making optical filtering.In certain embodiments, dielectric material comprises oxide (for example, metal oxide), fluoride (for example, metal fluoride), sulfide, and/or nitride (for example, metal nitride).The example of oxide comprises SiO 2, Al 2O 3, Nb 2O 5, TiO 2, ZrO 2, HfO 2, SnO 2, ZnO, ErO 2, Sc 2O 3, and Ta 2O 5The example of fluoride comprises MgF 2Other example comprises ZnS, SiN x, AlN, TiN, and HfN.Alternatively or additionally, these materials can comprise non-dielectric material, for example metal (for example, Al, Pt, Cu).
The example of high-index material comprises TiO 2, it has and is about 2.35 refractive index at 632nm, and Ta 2O 5, it has and is about 2.15 refractive index at 632nm.The example of low-index material comprises SiO 2And Al 2O 3, it has respectively at 632nm and is about 1.45 and 1.65 refractive index.
In certain embodiments, dielectric material is amorphous (for example, about 95% or more, about 98% or more, about 99% or more mostly be amorphous) substantially.Generally, non-crystalline material is optically isotropic and better with the dielectric layer light transmission that almost is crystal entirely than part.Yet, in certain embodiments, one or both dielectric materials partly or entirely can be for crystal.
The light transmission features of filter 10 can change according to some design parameters, comprising the quantity in each multilayer film middle level, and the optical thickness of each layer, the relative optical thickness of different layers, and the refractive index of each layer.In certain embodiments, filter can be designed as transmissive in certain wavelength width, basic all with the light of the interior incident of the conical surface of 50 one-tenth certain incident angles of optical axis, and the almost whole ultraviolet lights of wavelength outside this wavestrip of reflection, visible light, and/or infrared light (for example, all not from the light of about 200nm to the transmission wavestrip scope of about 2000nm).Substantially be called by the wavelength of filter transmission " passband wavelength ", and the wavestrip that is reflected is called " stopband wavelength ".The width of passband wavelength is broad (for example, from about 200nm to about 300nm or bigger) relatively, or can be narrower (for example, from about 0.4nm extremely about 20nm or littler).
Fig. 1 C illustrates an example of the transmitted spectrum of optical filtering.Curve C 1 correspondence is parallel to the transmitted spectrum that optical axis 50 is incident in the incident light on the optical filtering.Example hereto, the passband wavelength of light beam is corresponding to λ on the axle 1To λ 2Between wavelength, its corresponding optical filtering transmissive 50% incident light wavelength.In certain embodiments, the visible light part of the corresponding electromagnetic spectrum of the bandwidth of passband wavelength (for example, from about 400nm to about 700nm).The stopband wavelength can comprise infrared wavelength (for example, from about 700nm to about 2000nm).
In certain embodiments, optical filtering 10 can have high transmittance on some or all passband wavelength.For example, can reach about 95% or more (for example, 97% or more, about 98% or more, 99% or more, about 99.5% or more) to the transmissivity of passband wavelength.Usually, depend on the homogeneity and the degree of accuracy of the bed thickness of the adsorbability of the material that is used to form optical filtering and homogeneity and multilayer film in the transmittance of passband wavelength.For example, thus can reduce its transmittance by the light that absorption is incident in filter at the material that the passband wavelength has a higher relatively adsorbability.Heterogencity in the filter (for example, impurity and/or domain) can reduce transmittance by scatter incident light.The bed thickness deviation can cause the incident light generation coherent reflection of passband wavelength, thereby reduces its transmittance.Can further improve transmittance by the reflection loss that reduces the surface of contact place between optical filtering and the atmosphere.Compare with the optical filtering that only has one side to be coated with multilayer film, be set among the embodiment of substrate opposed surface, can reduce the reflectivity of transmission peak wavelength glazing at multilayer film.
Transmittance to all or part of stopband wavelength can be relatively low, and for example about 5% or still less (for example, about 4% or still less, about 3% or still less, about 2% or still less, about 1% or still less).Increase optical filtering and can reduce transmissivity the stopband wavelength to the reflectivity of these wavelength and adsorption rate.Increase the quantity in each multilayer film middle level and/or increase low-refraction and high refractive index layer between the difference of refractive index can increase the reflectivity of stopband wavelength.
In certain embodiments, optical filtering 10 can have a less blue shift at transmitted wave belt edge place for the light beam that is incident on non-perpendicular angle on the filter.The position of transmitted wave belt edge is 50% wavelength corresponding to filter transmission.In Fig. 1 C, the λ in these and the curve C 1 1And λ 2Corresponding.Because the optical thickness for the layer in each multilayer film of Axial Bundle changes, so these wavelength are generally as the function of the incident angle of light beam.The method line position at wavestrip edge is generally corresponding to vertical incidence light.Shorter wavelength is shifted to increase incident angle, i.e. " blue shift " in the wavestrip edge.The transmitted spectrum of filter when for example, the curve C 2 among Fig. 1 C illustrates light and is incident on filter to be not parallel to axle 50 angle.In this example, the position at wavestrip edge is from λ 1Shift to λ 1', and λ 2Shift to λ 2', wherein, λ 1'＜λ 1Move and λ 2'＜λ 2
So by selecting to have the amplitude that layer (for example, refractive index is about 1.7 or bigger, about 1.8 or bigger, about 1.9 or bigger, about 2.0 or bigger) that higher relatively refractive index materials forms optical filtering 10 reduces blue shift.In certain embodiments, when light and axle were spent angle incident for 50 one-tenths 30, blue shift can be 30nm or still less (for example, about 25nm or still less, about 23nm or still less, about 20nm or still less, about 18nm or still less, about 15nm or still less).
Generally, can prepare multilayer film on demand.In certain embodiments, can use atomic layer deposition method (ALD) preparation multilayer film 11 and 12.With reference to figure 2A, ALD system 100 is used for deposit multilayer film 11 and 12 on the surface 21 and 22 of substrate 20 respectively.Additional multilayer film 101 are deposited on the exposed surface 102.As selection, after depositing operation was finished, multilayer film 101 can be removed from substrate 20, to form optical filtering 10 (seeing Figure 1A ).Multilayer film 11,12 and deposition one deck of 101 connect the formation of one deck, and the composition and the thickness of film are effectively controlled.In the deposition process of individual layer, the steam of precursor can be introduced into reaction chamber and be attracted to substrate surface 11,12 and 102 or the layer of the former deposition on contiguous these surfaces on.Subsequently, with reactant introduce reaction chamber and with the precursor generation chemical reaction of absorption, thereby form the individual layer of material requested.This lip-deep chemical reaction can provide accurate control and provide large-area homogeneity to sedimentary deposit from the characteristic of restriction for film thickness.And precursor unoriented absorption on exposed surface can realize that material relative response chamber 110 from the teeth outwards has the uniform deposition of different orientation.
ALD system 100 comprises the reaction chamber 110 that links to each other with 190 by header 130 and source 150,160,170,180.Source 150,160,170,180 and 190 link to each other with header 130 with 191 by supply line 151,161,171,181 respectively.Valve 152,162,172,182 and 192 regulate the flow from the gas of source 150,160,170,180 and 190 respectively.Source 150 and source 180 comprise first precursor and second precursor respectively.And source 160 and source 190 comprise first reactant and second reactant respectively.Source 170 comprises carrier gas, constantly flows through reaction chamber 110 in deposition process, transmits precursor and reactant to substrate 20, and byproduct of reaction is sent away from substrate.Precursor and reactant are introduced into reaction chamber 110 by mixing with carrier gas in header 130.Gas is discharged reaction chamber 110 by outlet 145.Pump 140 is discharged reaction chamber 110 with gas by outlet 145.Pump 140 is connected with outlet 145 by pipe 146.
ALD system 100 comprises temperature controller 195, is used for controlling the temperature of reaction chamber 110.In deposition process, temperature controller 195 is elevated to the temperature of substrate 101 and is higher than ambient temperature.Usually, underlayer temperature should be enough high with the rapid reaction between promotion precursor and the reactant, but can not damage substrate.In certain embodiments, underlayer temperature can for about 500 ℃ or lower (for example, about 400 ℃ or lower, about 300 ℃ or lower, about 200 ℃ or lower, about 150 ℃ or lower, about 125 ℃ or lower, about 100 ℃ or lower).
Generally, the underlayer temperature great changes that between the different parts of substrate 20, do not have.Very big temperature variation can cause the variation of the reaction rate of precursor and reactant between the different parts of substrate, thereby causes the thickness that is deposited layer and/or the variation of tissue morphology.In certain embodiments, the temperature between the different parts of deposition surface differ about 40 ℃ or still less (for example, about 30 ℃ or still less, about 20 ℃ or still less, about 10 ℃ or still less, about 5 ℃ or still less).
The deposition process parameter is by electronic controller 199 controls and synchronous.Electronic controller 199 and temperature controller 195, pump 140, and valve 152,162,172,182 and 192 is communicated with.Electronic controller 199 also comprises user interface, and the person can be provided with deposition process parameters by this interface operation, the monitoring deposition process, and with system's 100 interactive operations.
With reference to figure 2B, ALD system start-up (1010), this moment, system 100 was by mixing first precursor first precursor from the source during 150 introducing reaction chambers 110 (1020) with carrier gas from source 170.Individual layer first precursor is adsorbed on the surface 21,22 and 102 of substrate 20, and the continued to flow carrier gas of reaction chamber of remaining precursor is removed (1030) from reaction chamber 110.Next, system introduces first reactant the reaction chambers 110 (1040) from source 160 by header 130.The individual layer of first reactant and first precursor reacts, and forms the individual layer of first material.As for first reactant, carrier gas stream with the reactant of remnants from chamber cleaning (1050).Repeating step 1020 to 1060 reaches desirable thickness (1060) until first material layer.
At film is among the embodiment of simple layer of material, promptly stops (1070) in case first material reaches desirable thickness technology.And be deposited under the situation that film is multilayer film, system can introduce reaction chamber 110 (1080) with second precursor by header 130.The individual layer of second precursor is attracted on the exposed surface of first material that is deposited, and carrier gas with residual precursor from chamber cleaning (1090).Then, system 180 introduces second reactant to reaction chamber 110 by header 130 from the source.The individual layer of second reactant and second precursor reacts, and forms the individual layer (1100) of second material.The carrier gas stream that flows through reaction chamber is removed (1110) with the reactant of remnants.Repeating step 1080 to 1110 reaches desirable thickness (1120) until second material layer.
Other layer except that first material and second material is deposited by repeating step 1020 to 1130.In case obtain the layer of requirement, technology stops (1140), and the substrate that will be deposited shifts out from reaction chamber 110.
Though precursor was introduced into reaction chamber before reactant in each circulation of technology as previously mentioned, in other embodiments, reactant also can be introduced into before precursor.The introducing of precursor and reactant order can be selected according to the interaction between they and the exposed surface.For example, when the binding energy on precursor and surface is higher than the binding energy on reactant and surface, can before reactant, introduce precursor.On the contrary, if the binding energy of reactant is higher, then can before precursor, introduce reactant earlier.
The thickness of each individual layer generally depends on some factors.For example, the thickness of each individual layer can depend on and be deposited type of material.Compare with the material that is made of less molecule, the material that is made of big molecule may cause thicker individual layer
Underlayer temperature also can influence the thickness of individual layer.For example, for some precursor, higher temperature can reduce precursor absorption from the teeth outwards in the deposition cycle, thus when causing forming with low underlayer temperature the thickness that should form compare thinner individual layer.
The type of precursor and the type of reactant, and the proportioning of precursor and reactant also can influence the thickness of individual layer.In certain embodiments, the individual layer of material can utilize specific precursor and differential responses thing deposition to obtain, for every kind of resulting thickness in monolayer difference of combination.Similarly, the single layer of material that is formed by different precursors can cause different thickness in monolayer because of different precursors.
Other example that influences the factor of thickness in monolayer comprises: remove the duration, and the residence time of precursor on coating surface, the pressure of reactor, the physical geometry form of reactor, and accessory substance is in the possible influence of deposition materials.The example that accessory substance influences film thickness is the material that the accessory substance corrosion is deposited.For example, when using precursor TiCl 4With reactants water depositing Ti O 2The time HCl be accessory substance.HCl can corrode the TiO that is deposited before it is drawn out of 2Corrosion can reduce the thickness of the individual layer that is deposited, and, if the specific part of substrate (for example is exposed to the longer time of HCl than other parts, may be from the nearer substrate of escape hole part than partly being exposed to the longer time of accessory substance from escape hole substrate far away), can cause that thickness in monolayer changes on the entire substrate.
Generally, the thickness of individual layer is approximately between 0.1nm and the about 5nm.For example, the thickness of one or more individual layers that are deposited can be about 0.2nm or more (for example, about 0.3nm or more, about 0.5nm or more).In certain embodiments, the thickness of one or more individual layers that are deposited can be about 3nm or more (for example, about 2nm or more, about 1nm or more, about 0.8nm or more about 0.5nm or more).
The average deposition thickness in monolayer can be determined so that material layer to be provided by the individual layer of deposition preset quantity on substrate.Next, measure the thickness be deposited layer (for example, by ellipsometry, electron microscope method, or some other methods).Then, the average deposition thickness in monolayer can be defined as the thickness of measured layer divided by number of deposition cycles.The average deposition thickness in monolayer is corresponding to theoretical monolayer thickness.Theoretical monolayer thickness is relevant with the characteristic dimension of the molecule that constitutes individual layer, and it can calculate by the volume density of material and the molecular weight of molecule.For example, SiO 2The estimated value of thickness in monolayer be about 0.37nm.This thickness is 2.0gcm by density -3Noncrystal SiO 2The cubic root of molecular cell estimate to obtain.
In certain embodiments, the average deposition thickness in monolayer corresponding to the mark of theoretical monolayer thickness (for example, 0.2 of about theoretical monolayer thickness, 0.3 of about theoretical monolayer thickness, 0.4 of about theoretical monolayer thickness, 0.5 of about theoretical monolayer thickness, 0.6 of about theoretical monolayer thickness, 0.7 of about theoretical monolayer thickness, 0.8 of about theoretical monolayer thickness, about theoretical monolayer thickness 0.9).Perhaps, the average deposition thickness in monolayer can be corresponding to more than a times of theoretical monolayer thickness, (for example be about 30 times of theoretical monolayer thickness at most, 2 times of about theoretical monolayer thickness or more, 3 times of about theoretical monolayer thickness or more, 5 times of about theoretical monolayer thickness or more, 8 times of about theoretical monolayer thickness or more, 10 times of about theoretical monolayer thickness or more, 20 times of about theoretical monolayer thickness or more).
In deposition process, the pressure of reaction chamber 110 can remain basic constant voltage, maybe can change.Usually can control air pressure by control by the speed of the carrier gas stream of reaction chamber.Generally, air pressure should enough highly make the surface soak into chemical absorbing substance with the permission precursor, and the surface mass complete reaction that allows reactant and precursor to stay also stays response location for next round-robin precursor.If the dosage of precursor and/or reactant is low excessively, and/or the speed of pump is too fast, and it is low excessively chamber pressure to occur, and the surface may not be soaked into by precursor and react may not be from restriction.This situation may cause the in uneven thickness of sedimentary deposit.And the pressure of reaction chamber can not be too high so that the removal of the reaction product that the reaction of obstruction precursor and reactant produces.Remaining accessory substance may hinder soaking into of when the next round precursor is introduced into reaction chamber surface.In certain embodiments, chamber pressure is maintained at about (for example, between about 0.1Torr and about 20Torr, between about 0.5Torr and about 10Torr, such as about 1Torr) between 0.01Torr and the about 100Torr.
Usually, the precursor of introducing in each circulation and/or the amount of reactant can be according to the sizes of reaction chamber, the area of exposed substrate surface, and/or chamber pressure is selected.The precursor of introducing in each circulation and/or the amount of reactant can be selected according to experience.
The precursor of introducing in each circulation and/or the amount of reactant can be controlled by the time of control opening and closing valve 152,162,172,182 and 192.The precursor of introducing and the amount of reactant are relevant with the time quantum of each valve opening in each circulation.Valve should be opened long enough and cover so that enough individual layers to be provided at substrate surface to introduce enough precursors.Similarly, the amount of the reactant of introducing in each circulation should be enough and all precursors that are deposited on the exposed surface fully react.Introducing can prolong cycling time and/or waste precursor and/or reactant more than the precursor and/or the reactant of requirement.In certain embodiments, the dosage of precursor can corresponding to each circulation with between the suitable valve open about 0.1 second and about 5 seconds (for example, about 0.2 second or more, about 0.3 second or more, about 0.4 second or more, about 0.5 second or more, about 0.6 second or more, about 0.8 second or more, about 1 second or more).Similarly, the dosage of reactant is with to open suitable valve relevant, each circulation between 0.1 second and about 5 seconds (for example, about 0.2 second or more, about 0.3 second or more, about 0.4 second or more, about 0.5 second or more, about 0.6 second or more, about 0.8 second or more, about 1 second or more).
Precursor is relevant with removing with the time between reactant is batched.Each reset procedure answers long enough so that residual precursor or Residual reactants are removed from reaction chamber, if but need the time long then can unnecessarily increase cycling time than this.The time spent of the different reset procedurees in each circulation can be identical also can be different.In certain embodiments, the time of removing be about 0.1 second or more (for example, about 0.2 second or more, about 0.3 second or more, about 0.4 second or more, about 0.5 second or more, about 0.6 second or more, about 0.8 second or more, about 1 second or more, about 1.5 seconds or more, about 2 seconds or more).Generally, checkout time be about 10 seconds or still less (for example, about 8 seconds or still less, about 5 seconds or still less, about 4 seconds or still less, about 3 seconds or still less).
Time between precursor is in succession batched is relevant with cycling time.Round-robin for the individual layer that deposits different materials cycling time can be identical or different.And, for the individual layer of deposition same material, but use the round-robin situation of different precursors and/or differential responses thing, cycling time can be identical or different.In certain embodiments, cycling time can be for about 20 seconds or still less (for example, about 15 seconds or still less, about 12 seconds or still less, about 10 seconds or still less, about 8 seconds or still less, about 7 seconds or still less, about 6 seconds or still less, about 5 seconds or still less, about 4 seconds or still less, about 3 seconds or still less).Reduce the time that can reduce deposition process cycling time.
The selection of precursor generally will make compatible mutually with ALD technology, and can be by providing required deposition materials with reactant reaction.In addition, precursor and material should be compatible mutually with the material that will deposit thereon (for example, with backing material or the sedimentary deposit that forms previously).The example of precursor comprises: chloride (for example, metal chloride), for example TiCl 4, SiCl 4, SiH 2Cl 2, TaCl 3, HfCl 4, InCl 3And AlCl 3In certain embodiments, organic compound can be used as precursor (for example, ethanolato-titanium, ethoxy thallium and ethoxy niobium).Another example of organic compound precursor is (CH 3) 3Al.
The selection of reactant generally also will make compatible mutually with ALD technology, and selects according to the chemical property of precursor and material.For example, if material is an oxide, reactant can be an oxygenant.The example of the oxygenant that is fit to comprises: water, hydrogen peroxide, oxygen, ozone, (CH 3) 3Al and various alcohols (for example, ethanol CH 3OH).For example, water is a kind of suitable reactant as for TiCl for the oxidized form precursor 4Can obtain TiO 2, for AlCl 3Can obtain Al 2O 3, can obtain Ta for the ethoxy thallium 2O 5, can obtain Nb for the ethoxy niobium 2O 5, for HfCl 4Can obtain HfO 2, for ZrCl 4Can obtain ZrO 2, and for InCl 3Can obtain In 2O 3In each case, HCl can produce as accessory substance.In certain embodiments, (CH 3) 3Al can be used to the monox alkanol to obtain SiO 2
With reference to figure 3, as previously discussed, except the multilayer film 11 and 12 that form on surface 21 and 22 respectively, ALD technology also forms multilayer film at the edge surface 101 of substrate 20.Because ALD technology, multilayer film 101 have identical composition and thickness with multilayer film 11 and 12, and link to each other with 12 with multilayer film 11.And each layer in the multilayer film 101 and multilayer film 11 link to each other with equivalent layer in 12.Fig. 3 illustrates a such layer, layer 303.Layer 303 have with multilayer film 11 in equivalent layer 301 and same composition and the thickness of the equivalent layer in the multilayer film 12 302.
In certain embodiments, ALD can be used for covering substantially all surfaces of substrate, promptly coats substrate.It can be by exposing some surf zones of substrate in initial ALD process, and the surf zone that covers retention in second ALD process is realized, wherein, in second ALD process, the direction of substrate is changed to expose the surf zone of front crested in the reaction chamber.As selection, the surface that is capped in ALD process early can crested in second process, has deposited basic the same quantity of material like this on each surface.Perhaps, the surf zone that is not capped in initial ALD process can be sealed with other covering method.When backing material was easy to by environmental damage and/or film forming material the harm of environment is had special resistant function, it was useful coating substrate.
Although described specific embodiment, other embodiment also is feasible.
As example, although described use ALD systems produce IR light filter film, ALD also can be used to form the film of other type, for example, antireflecting film, ultraviolet cut-on filter, narrow-band filter, DWDM optical filtering, phase compensator, high reflection mirror, and/or ducting layer.
As another example, although described the film of the number of plies with some, more generally, film can have one or more layers (for example, 2,3,4,5,6,7,8,9,10,11,12,13,14,15 layers).Usually, the number of plies of multilayer film is selected according to the optical characteristics of required film.(for example, multilayer film comprise having different heat-mechanical properties (for example, different thermal expansivity) material), and the film of a lot of layers may stand bigger mechanical pressure than the film with less number of plies in the thermal cycle process in certain embodiments.In certain embodiments, multilayer film may surpass 15 layers (for example, about 20 layers or more, about 30 layers or more, about 40 layers or more, about 50 layers or more).
Although to 1000nm, ALD can be used to deposit the thin layer that exceeds this scope to the scope of the layer thickness of multilayer film 11 and 12 from about 20nm.These layers can be as thin as an individual layer (for example, about 0.3nm is to about 2nm), and are thick in several thousand nanometers (for example, about 2000nm or more, about 3000nm or more, about 5000nm or more).For example, in certain embodiments, one or more layers thickness can be significantly less than optical wavelength (for example, significantly less than 200nm).For example, certain layer can have about 20nm or thickness still less (for example, about 15nm or still less, about 10nm or still less, about 8nm or still less, about 5nm or still less, about 2nm or still less).In certain embodiments, the thickness of one deck can be for the thickness of about 20 individual layers of material or still less (for example, the thickness of about 15 individual layers or still less, the thickness of about 10 individual layers or still less, the thickness of about 8 individual layers or still less, the thickness of about 5 individual layers or still less, the thickness of about 3 individual layers or still less, the thickness of about 2 individual layers, the thickness of about 1 individual layer), wherein thickness in monolayer refers to the desirable thickness in monolayer that discuss the front.Bed thickness in the film is during significantly less than optical wavelength, and the optical characteristics of film will be the mean value of the optical characteristics (for example refractive index) of the material that constitutes film.Comprise that significantly the film less than the material layer of optical wavelength is known as nano-stack.In certain embodiments, the part of film or a plurality of part can be nano-stack.Nano-stack partly can be used as the layer with homogeneous refractive index, and this refractive index is effective mean value of the refractive index of the material of formation nano-stack.In certain embodiments, nano-stack can be used for forming the graded index part in multilayer film.The example of nano-stack part comprises by SiO 2Individual layer and TiO 2Individual layer, or SiO 2Individual layer and Ta 2O 3The part that individual layer forms.
In addition, although each in multilayer film 11 and 12 all is made of the layer of two kinds of different materials, film may comprise the layer more than two kinds of different dielectric materials usually.For example, although all high refractive index layers in described embodiment are formed by same material, usually high refractive index layer can by of the same race or not same material form.Similarly, low refractive index material layer can be formed by of the same race or different materials.Generally, the quantity of the different material layer in multilayer film can change according to need.
In addition, form multilayer film 11 and 12 individual layer each all form by single dielectric material of planting, and in certain embodiments, the composition of sedimentary deposit can comprise more than a kind of material.For example, enter reaction chamber 110, can form the individual layer that comprises two or more different materials by introducing simultaneously more than a kind of precursor.The composition of each individual layer in one deck can adapt to the index distribution in the film and change.
Film 11 and 12 is continuous on whole surperficial 21 and 22, and in certain embodiments, uses the film possibility discontinuous (for example, patterned) of ALD preparation on the surface.Composition can be carried out in the ALD technological process or after it.In the ALD process, carry out among the embodiment of composition, can not adhere to the some parts of the material processed substrate on it with precursor and/or reactant.Do not have material to be deposited over these parts, and ALD technology with material layer depositions at unprocessed portion.For example, hydrophobic material as the teflon spraying, can be capped on surface portion, to reduce the absorption of surface to water.Perhaps, or in addition, the substrate surface part can be hidden by a material of removing after deposition, the film portion that deposits thereon in order to the place to go.
Can use for example photoetching composition on post-depositional film.For example, can cover optical filtering with resist, subsequently will be on this resist composition and this resist of etching to expose film portion.The etching exposed part also removes remaining resist subsequently, thereby produces the film that contains figure.
Though the optical flat of substrate 10 for being made of glass, usually, the composition of substrate and shape can change.Generally, can form substrate with any material compatible mutually with being deposited material, precursor, reactant and laydown adjustment.The backing material that is fit to comprises glass (for example, actinic glass, quartz, soda-lime glass, glass ceramics), metal (for example, aluminium, stainless steel, nickel, copper), semiconductor (for example, silicon, germanium), and/or polymkeric substance, for example thermosetting polymer and thermoplastic polymer.The example of polymkeric substance comprises polycarbonate, polyester, polypropylene, acrylic, liquid crystal polymer, tygon phthalandione, polyamide, polyvinylchloride rope, and tygon.
Substrate may comprise the material to high temp. sensitive, may be damaged in the high temperature if be exposed to.In this case, underlayer temperature is in deposition process, and should not be increased to can be to the hurtful temperature of substrate.In certain embodiments, backing material for be about 150 ℃ or higher (for example, about 170 ℃ or higher, about 200 ℃ or higher, about 300 ℃ or higher, about 400 ℃ or higher, about 500 ℃ or higher) the temperature potentially unstable.Backing material may stand not expect when for example, surpassing uniform temperature physics and/or chemical change.An example of the physical change of not expecting is phase transformation.For example, the liquid crystal polymer substrate may become isotropic after surpassing uniform temperature.Glassy transition may take place in some backing materials (for example, some polymkeric substance) when surpassing uniform temperature.For example, substrate may comprise glass transition temperature be about 150 ℃ or higher (for example, about 200 ℃ or higher, about 300 ℃ or higher, about 400 ℃ or higher, about 500 ℃ or higher) material.The oxidation that an example of chemical change is a backing material (for example, the oxidation of copper substrate).
Backing material can have and one or more similar thermo-mechanical properties of material that are used to form film.For example, the thermal expansivity of backing material (CTE) can be similar to the CTE of one or more materials that are used to form film.In certain embodiments, in order to form film in the circular treatment substrate temperature scope (for example) from about 0 ℃ to about 300 ℃, the CTE of backing material may for the CTE of the material that is used to form film 10% or still less (for example, about 8% or still less, about 5% or still less).The thermo-mechanical property of material can reduce the mechanical stress in the film in the thermal cycle process in coupling substrate and the film, otherwise this mechanical stress may cause film breaks or other damage.
In certain embodiments, substrate may be the part of optical element or optical element.Optical element comprises refracting element (for example, lens), diffraction element (for example, diffraction grating), reverberator (for example, catoptron), and light-emitting component (for example, light emitting diode, laser instrument).
In certain embodiments, the substrate surface that uses ALD to cover can be general plane, for example surface 21 and 22 of substrate 10.Here, the surface of general plane has 100 meters or bigger radius-of-curvature.Perhaps, the surface that is capped may be for bending.Curved surface has the radius-of-curvature less than 100 meters.In certain embodiments, the surface may be patterned surface (Structured surface).Patterned surface refers to have uncontinuity in the surface normal direction.Patterned surface can have the part on plane and/or the part of curved surface.An example with substrate of curved surface is lens, as the lens among Fig. 4 401.The curved surface 411 and 421 of lens 401 is covered by film 410 and 420 by ALD respectively.Film 410 is similar to 421 with surface 411 to 420, has homogeneous thickness on each surface.Film 410 and 420 may comprise the simple layer or the multilayer of different component.410 and 420 is among the embodiment of multilayer film, and each layer in the multilayer film can have uniform thickness on whole film.Film 410 and 420 can be identical or different.For example, for example, similar with aforesaid film 11 and 12, two films can constitute optical filtering.In another optional example, film 10 can be optical filtering, and film 420 can be antireflecting film.In the identical embodiment of above-mentioned film, can in ALD technology,, surface 411 and 421 form above-mentioned film simultaneously by all being exposed.
Usually, use the curvature on the surface of ALD covering to change.In certain embodiments, substrate can have suitable curved surface, and has relatively large radius-of-curvature, for example about 1 meter or more (for example, about 2 meters or more, about 3 meters or more, about 5 meters or more, about 10 meters or more, about 20 meters or more).Example with substrate surface of low curvature comprises some lens, for example the certain lenses of using in the glasses.Perhaps, in some cases, substrate surface can have higher curvature, and can have less relatively radius-of-curvature, for example about 10cm or littler (for example, about 8cm or littler, about 5cm or littler, about 3cm or littler, about 2cm or littler, about 1cm or littler, about 0.5cm or littler, about 0.1cm or littler).Example with substrate surface of higher curvature comprises various lens, for example globe lens.
In certain embodiments, substrate can comprise the patterned surface that the film of one or more use ALD preparation covers.With reference to figure 5, the surface 520 that an example of patterned surface is a Fresnel lens 501.ALD is used in deposit film 510 (for example, simple layer or multilayer film) on 520 slope 521, surface and inclined-plane (draft) 522.The conformal nature of ALD technology causes film 510 all to have roughly homogeneous thickness on slope 521 and inclined-plane 522.In certain embodiments, film 510 is an antireflecting film, and it can reduce (for example, eliminating) and not use the ghost effect that can not occur under the situation of these lens.
Can use other example of the patterned surface that ALD covers to comprise optical grating construction, for example ruling grating and relief grating, cylindrical surface, for example inside surface of optical fiber surface or hollow waveguide (for example, having circle, square or square-section).What another was exemplified as optical fiber splits branch (cleaved) surface.For example, adopt cutting optical fibre to be positioned to be close to the design proposal of lens or optical module in some communication applications.Use ALD can reduce the reflectivity of film at cutting surface coverage AR film.Can in an ALD operation, cover a plurality of cuttings surface.
The optical module that uses method described here to make can be used for various optical systems.With reference to figure 6, in certain embodiments, use the IR filter 610 of ALD fabrication techniques to be used to imaging system 600.Imaging system comprises lens 620 and 630, and it will be propagated and photoimaging by aperture 640 looks like on the detector 650 (for example, charge (CCD) or complementary metal oxide semiconductor (CMOS) (CMOS) detector) on plane to being in along axle 660.IR filter 610 is arranged between lens 620 and the detector 650.IR filter 610 comprises multilayer film 611 and 612, and the amount that aperture 640 is radiated at the IR light on the detector 650 is passed in its minimizing (for example, the basic elimination).For example, the IR filter can reduce about 20% or the light quantity of the stopband wavelength of more (for example, about 50% or more, about 80% or more, about 90% or more, about 95% or more).In certain embodiments, IR filter 610 has and the similar transmitted spectrum of spectrum shown in Fig. 1 C.
In certain embodiments, can use ALD that optical module is integrated into optical system.For example, can replace discrete IR filter 610 in the imaging system 600 with the one or more surfaces that filter directly are covered in the lens in the imaging system.For example, with reference to figure 7, imaging system 700 comprises a pair of lens 720 and 730, and this will propagate and pass the photoimaging of aperture 740 on detector 750 along axle 760 to lens.Optical filtering 710 comprises the multilayer film 713,714,711 and 712 on the surface 721,722,731 and 732 that is deposited on lens 720 and 730 respectively.Be similar to IR filter 610 as shown in Figure 6, optical filtering 710 can reduce (for example, the basic elimination) and pass the amount that aperture 740 is radiated at the IR light on the detector 750.
In another embodiment, Fig. 8 illustrates imaging system 800, this system comprise be deposited on lens 820 single surperficial 821 on IR filter 810.Imaging system 800 also comprises second lens 830, detector 850 and aperture 840.Lens 820 and 830 will pass the photoimaging of aperture 840 to detector 850.Surface 821 is corresponding to the lens surface at the minimum place of divergence of imaging light.In other words, the maximum difference of the imaging light direction of propagation is less than the maximum difference of other lip-deep imaging light direction of propagation of lens 720 and 730.Therefore, when filter is positioned at surperficially 810 the time, the maximum blue shift amount of filter band edge is less than other the lip-deep blue shift amount that is located in imaging system 800.
The divergence of beam degree is illustrated by light 860 and 870, common point 851 places that it comes from the common point light source and is imaged on detector 850.Light 860 and 870 angle of propagation with respect to the optical axis 899 of imaging system 800 are respectively φ 1And φ 2The divergence of light is φ 1And φ 2Difference.In certain embodiments, the light of imaging beam have at IR filter 810 places be about 20 the degree or maximum divergence still less (for example, be about 15 the degree or still less, be about 10 the degree or still less, be about 8 the degree or still less).Therefore, system edges light is compared generation with the light of propagating along axle 899 blue shift amount for about 20nm or still less (for example, about 15nm or still less, about 12nm or still less, about 10nm or still less).
In another embodiment, Fig. 9 illustrates a kind of imaging system 900, and it comprises the IR filter 910 on the surface 951 that is deposited on detector 950 (for example, CCD or cmos detector).Imaging system 900 also comprises lens 920, second lens 930 and aperture 940. Lens 920 and 930 will pass the photoimaging of aperture 940 to detector 950.
Imaging system can be used in the electronic equipment such as digital camera and Digital Video as previously discussed.In certain embodiments, imaging system can be used to the digital camera in the mobile phone.
Below be exemplified as illustrative, unrestriction.
Example
Example I
Can be made into optical filtering by the two opposite sides deposit multilayer film at BK7 optical flat (diameter 100mm), this BK7 light flat board can obtain from Abrisa company (California, USA Santa Paula city).Use H 2O:H 2O 2: NH 4OH solution cleans this optical flat, with the organic pollutant of removal slightly solubility, and uses H 2O:H 2O 2: HCl solution removal ion and heavy metal atom pollutant.High-index material is TiO 2, low-index material is AL 2O 3The precursor of high-index material is an ethanolato-titanium, and purity is 99.999%, obtains from Sigma-Aldrich company (St. Louis city).The precursor of low-index material is (CH 3) Al, purity also is 99.999%, obtains from Sigma-Aldrich company (St. Louis city).For these two kinds of materials, reactant is deionized water, can obtain by the deionizater that uses Allied Water Technologies company (Danbury city, U.S. Kang Naitige state).
Optical flat is positioned over the Systems from Planar, in the P400A ALD reaction chamber that Inc. company (Ore. is than Fu Dun city) obtains, in order to the deposit multilayer film.Vacuumize in the reaction chamber.Nitrogen flows through reaction chamber, and keeping the reaction chamber internal gas pressure is about 1Torr.Reaction chamber temperature is set at 170 ℃ and wait for about 7 hours so that substrate temperature balance.In case reach temperature balance, supply valve 0.7 second is introduced reaction chamber with the pulse of initial water steam by fetching boiling water.After the water supply valve cuts out, feed nitrogen 3 seconds to purify reaction chamber.Next, open (CH 3) Al valve 0.8 second, with (CH 3) Al introduces reaction chamber.Before another water vapor of taking turns is introduced into, introduce nitrogen 1.5 seconds once more to purify reaction chamber.Between purified treatment, alternately introduce water vapor (0.7 second) and (CH 3) Al (0.8 second), cause on the exposed surface of substrate, forming Al 2O 3Layer.The whole circulation time is 7 seconds.Repeat this circulation 95 times, the result obtains one and has the Al that thickness is 9.56nm 2O 3Layer.
In depositing Al 2O 3Behind the layer, in the pulse process in two seconds, water vapor is introduced into reaction chamber.Next be two seconds purification run, one second ethanolato-titanium, and two seconds purification run again.This circulation is repeated 172 times, and the result obtains one and is deposited on Al 2O 3Thickness on the layer is about the TiO of 6.48nm 2Layer.
Use other Al of above-mentioned deposition 2O 3And TiO 2The step of layer is produced multilayer film at exposed substrate surface.The number of deposition cycles that table 1 has gathered the thickness of each layer and has been used for depositing each layer.
With reference to Figure 10, use λ 14UV/Vis spectrometer to detect the performance of optical filtering, this spectrometer obtains from Perkin-Elmer company (Massachusetts, United States Wellesley city).Measure incident angle and be the transmitted spectrum of the optical filtering under 0 ° and the 30 ° of situations.In the time of 0 °, passband extends to about 680nm from about 380nm.Transmissivity to these wavelength is about 90%.Optical filtering stops the light from about 690nm to about 1100nm wavelength basically.When incident angle was 30 °, band edge moved about 20nm from 680nm, reached about 650nm.
Example II
Utilize and make optical filtering as the described method of example I, high-index material is TiO 2, low-index material is Al 2O 3The precursor of high-index material is an ethanolato-titanium, and the precursor of low-index material is TMA.For two kinds of materials, reactant is deionized water.
At the beginning, deposit the thick Al of a 307.7nm 2O 3Cushion.Form this layer by 3045 ALD circulations.Table II has gathered the thickness of each extra play, and is used to deposit every layer number of deposition cycles.Cycle index identical with described in the example I.
With reference to Figure 11, use spectrometer to detect the performance of optical filtering.Optical filtering transmitted spectrum when measuring 0 °.When 0 ° of incident, passband extends to about 650nm from about 390nm.To the transmissivity of these wavelength between about 92% to about 94%.Optical filtering stops the light from about 670nm to about 1100nm wavelength basically.
Other embodiment is referring to claims.
Table I
Figure A200580008868D00361
Table II
Figure A200580008868D00371

Claims (132)

1. goods, it comprises:
Substrate, the second surface that it has first surface and links to each other with first surface, first surface and second surface be coplane not;
Be deposited on first multilayer film on the first surface;
Be deposited on second multilayer film on the second surface, wherein, described second multilayer film link to each other with described first multilayer film.
2. goods as claimed in claim 1, wherein, described first multilayer film and second multilayer film comprise the successive layers of first material.
3. goods as claimed in claim 2, wherein, described first multilayer film and second multilayer film comprise the successive layers of second material, wherein, second material is different from first material, and the first material successive layers supports the second material successive layers.
4. goods as claimed in claim 1, wherein, described first multilayer film and second multilayer film comprise 3 or more successive layerss, wherein, adjacent layer is formed by different materials.
5. goods as claimed in claim 1, wherein, described substrate is an optical module.
6. goods as claimed in claim 5, wherein, described optical module is lens.
7. goods as claimed in claim 6, wherein, described lens are Fresnel lens.
8. goods as claimed in claim 5, wherein, described optical module is an optical flat.
9. goods as claimed in claim 1, wherein, described substrate comprises glass.
10. goods as claimed in claim 9, wherein, described glass is selected from optical glass, glass-ceramic, quartz, silica glass and soda-lime glass.
11. goods as claimed in claim 1, wherein, described substrate comprises polymkeric substance.
12. goods as claimed in claim 11, wherein, described polymkeric substance is a thermosetting polymer.
13. goods as claimed in claim 11, wherein, described polymkeric substance is the thermoplastic polymer.
14. goods as claimed in claim 11, wherein, described polymkeric substance is selected from polysilicates, acrylic, polyester, tygon, polypropylene, Polyvinylchloride and poly-methyl acrylic methyl esters.
15. goods as claimed in claim 1, wherein, described substrate comprises that glass transition temperature is about 80 ℃ or lower material.
16. goods as claimed in claim 1, wherein, described substrate comprises that glass transition temperature is about 100 ℃ or lower material.
17. goods as claimed in claim 1, wherein, described substrate comprises that glass transition temperature is about 150 ℃ or lower material.
18. goods as claimed in claim 1, wherein, described substrate comprises that glass transition temperature is about 200 ℃ or lower material.
19. goods as claimed in claim 1, wherein, described substrate comprises that glass transition temperature is about 250 ℃ or lower material.
20. goods as claimed in claim 1, wherein, described substrate is included in 10% the backing material that 0 ℃ of thermal expansivity between 300 ℃ the time is the first material coefficient of thermal expansion coefficient.
21. goods as claimed in claim 1, wherein, described surface has about 100 meters or littler radius-of-curvature.
22. goods as claimed in claim 1, wherein, described surface is roughly the plane.
23. goods as claimed in claim 1, wherein, described surface is a patterned surface.
24. goods as claimed in claim 1, wherein, described first material is a dielectric material.
25. goods as claimed in claim 1, wherein, described first material is an oxide.
26. goods as claimed in claim 25, wherein, described oxide is a metal oxide.
27. goods as claimed in claim 26, wherein, described metal oxide is from SiO 2, Al 2O 3, Nb 2O 5, TiO 2, ZrO 2, HfO 2, and Ta 2O 5The middle selection.
28. goods as claimed in claim 2, wherein, described successive layers has and is about 1nm or bigger vertical optical thickness.
29. goods as claimed in claim 2, wherein, described successive layers has and is about 10nm or bigger vertical optical thickness.
30. goods as claimed in claim 2, wherein, described successive layers has and is about 20nm or bigger vertical optical thickness.
31. goods as claimed in claim 2, wherein, described successive layers has and is about 5000nm or littler vertical optical thickness.
32. goods as claimed in claim 2, wherein, described successive layers has and is about 1000nm or littler vertical optical thickness.
33. goods as claimed in claim 2, wherein, described successive layers has and is about 500nm or littler vertical optical thickness.
34. goods as claimed in claim 1, wherein, described first multilayer film and second multilayer film are antireflection film.
35. goods as claimed in claim 1, wherein, described goods are optical filtering.
36. goods as claimed in claim 35, wherein, described optical filtering is infrared filter.
37. goods as claimed in claim 36, wherein, described infrared filter reduces the optical transmission rate of wavelength from about 650nm to about 1100nm by described goods.
38. goods as claimed in claim 35, wherein, described optical filtering is the ultraviolet filter.
39. goods as claimed in claim 38, wherein, described ultraviolet filter reduces wavelength by described goods less than the optical transmission rate of about 400nm.
40. goods as claimed in claim 3, wherein, the refractive index of described first material is different from the refractive index of second material.
41. goods as claimed in claim 3, wherein, the vertical optical thickness of the successive layers of described first material is identical with the vertical optical thickness of the successive layers of second material.
42. goods as claimed in claim 3, wherein, the vertical optical thickness of the successive layers of described first material is different from the vertical optical thickness of the successive layers of second material.
43. goods as claimed in claim 1 also comprise the 3rd lip-deep the 3rd multilayer film that are arranged at substrate, described the 3rd surface is opposite with first surface.
44. goods as claimed in claim 43 are wherein described the first, the second, are identical with the 3rd multilayer film.
45. goods, it comprises:
Optical module, its have first surface and with the first surface opposed second surface;
Be deposited on first material layer on the first surface; With
Be deposited on first material layer on the second surface,
Wherein, on the described first surface vertical optical thickness of certain position place first material layer the vertical optical thickness of corresponding position first material layer on the described second surface about 5% in.
46. goods, it comprises:
Substrate, it has a radius-of-curvature and is about 10 meters or surface still less, wherein, described surface has first and second positions, and the angle between the surface normal of described first and second positions be about 2 the degree or still less; And
Be deposited on lip-deep film,
Wherein said film comprises first material layer, described layer the vertical optical thickness of primary importance be described layer the vertical optical thickness of the second place about 1% within.
47. goods, it comprises:
Substrate, its have first surface and with the first surface opposed second surface;
Be deposited on the first film on the first surface; With
Be deposited on second film on the second surface,
Wherein, on the described first surface vertical optical thickness of the first film at primary importance place the vertical optical thickness of second film of corresponding position on the second surface about 5% in.
48. goods, it comprises:
The substrate that comprises polymkeric substance; With
Be arranged at the multilayer film on the first surface of substrate.
49. an optical filtering, it comprises:
Limit the multilayer film of optical axis, wherein
The wavelength of propagating along optical axis of optical filtering transmission 50% is λ 1Light, and
The wavelength that becomes 30 degree angles to be incident on the multilayer film with optical axis of optical filtering transmission 50% is λ 2Light, wherein, | λ 1-λ 2| be about 30nm or still less.
50. optical filtering as claimed in claim 49, wherein λ 1Be about 650nm.
51. a film forming method on substrate, it comprises:
By the individual layer of a plurality of first materials of sequential aggradation, form first material layer, one of individual layer of described first material is deposited on the first surface of substrate,
Wherein, described film comprises first material layer, and substrate comprises polymkeric substance.
52. method as claimed in claim 51, wherein, the individual layer that deposits described a plurality of first materials comprises the individual layer of precursors to deposit and the individual layer of precursor is exposed in the reactant, to form the individual layer of first material.
53. method as claimed in claim 52, wherein, reactant and precursor generation chemical reaction are to form first material.
54. method as claimed in claim 53, wherein, reactant oxidation precursor is to form first material.
55. method as claimed in claim 52, wherein, the individual layer of precursors to deposit comprises introduces first gas that comprises described precursor in the reaction chamber of accommodating substrates.
56. method as claimed in claim 55, wherein, the pressure of first gas in the reaction chamber is that about 0.01Torr is to about 100Torr.
57. method as claimed in claim 55 wherein, is exposed to reactant with the individual layer of precursor and comprises to reaction chamber and introduce second gas that comprises reactant.
58. method as claimed in claim 57, wherein, the pressure of second gas is that about 0.01Torr is to about 100Torr in the reaction chamber.
59. method as claimed in claim 57 wherein, after first gas is introduced and before the introducing of second gas, is introduced the 3rd gas to reaction chamber.
60. method as claimed in claim 59, wherein, the 3rd gas is inertia for precursor.
61. method as claimed in claim 59, wherein, the 3rd gas comprises at least a gas of selecting from helium, argon, nitrogen, neon, krypton and xenon.
62. method as claimed in claim 52, wherein, precursor is from three (tert-butyl group) silanol, (CH 3) 3Al, TiCl 4, SiCl 4, SiH 2Cl 2, TaCl 3, AlCl 3, ethoxy hafnium and ethoxy thallium, middle selection.
63. method as claimed in claim 51, wherein, first material is a dielectric material.
64. method as claimed in claim 51, also comprise: the individual layer by a plurality of second materials of sequential aggradation is to form second material layer, one of individual layer of described second material layer is deposited on first material layer, wherein said second material is different from described first material, and film comprises described second material layer.
65., wherein, deposit a plurality of second single layer of material and comprise: the individual layer of precursors to deposit and the individual layer of described precursor is exposed in the reactant to form the individual layer of second material as the described method of claim 64.
66. as the described method of claim 65, wherein, reactant and precursor generation chemical reaction are to form second material.
67. as the described method of claim 66, wherein, reactant oxidation precursor is to form second material.
68. as the described method of claim 65, wherein, the individual layer of precursors to deposit comprises introduces first gas that comprises described precursor in the reaction chamber of accommodating substrates.
69. as the described method of claim 68, wherein, the pressure of first gas in the reaction chamber is that about 0.01Torr is to about 100Torr.
70., wherein, the individual layer of precursor is exposed to reactant comprises to reaction chamber and introduce second gas that comprises reactant as the described method of claim 68.
71. as the described method of claim 70, wherein, the pressure of second gas in the reaction chamber is that about 0.01Torr is to about 100Torr.
72. as the described method of claim 70, wherein, after first gas is introduced and before the introducing of second gas, reaction chamber is cleaned gas purification.
73. as the described method of claim 72, wherein, Purge gas is an inertia for first precursor.
74. as the described method of claim 72, wherein, Purge gas comprises at least a gas of selecting from helium, argon, nitrogen, neon, krypton and xenon.
75. as the described method of claim 65, wherein, precursor is from three (tert-butyl group) silanol, (CH 3) 3Al, TiCl 4, SiCl 4, SiH 2Cl 2, TaCl 3, AlCl 3, select in ethoxy hafnium and the ethoxy thallium.
76. as the described method of claim 64, wherein, second material is a dielectric material.
77. as the described method of claim 64, also comprise: form the 3rd material layer on the surface of second material layer, wherein, described the 3rd material is different from second material and film comprises described the 3rd material layer.
78. as the described method of claim 77, wherein, described the 3rd material is identical with first material.
79., wherein, use the method for ald to deposit the 3rd material layer as the described method of claim 77.
80. as the described method of claim 77, also comprise: form the 4th material layer on the surface of described the 3rd material layer, wherein, described the 4th material is different from the 3rd material and film comprises described the 4th material layer.
81. as the described method of claim 80, wherein, described the 4th material is identical with second material.
82., wherein, use the method for ald to deposit the 4th material layer as the described method of claim 80.
83., also comprise: form the extra play that supports by the 4th material layer as the described method of claim 80.
84. as the described method of claim 83, wherein, some in the extra play comprise first material or second material at least.
85., wherein, use the method for ald to form extra play as the described method of claim 83.
86. method as claimed in claim 51, wherein, described substrate is an optical module.
87. method as claimed in claim 51 also comprises: form first material layer on the second surface of substrate, simultaneously, form first material layer on first surface, wherein, described second surface is opposite with described first surface or continuous.
88. as the described method of claim 87, wherein, the individual layer by a plurality of first materials of sequential aggradation is to form first material layer at second surface, one of individual layer of described first material layer is deposited on the second surface of substrate.
89. as the described method of claim 64, also comprise:, simultaneously, on first material layer on the first surface, form second material layer being deposited on formation second material layer on first material layer of substrate second surface, wherein, described second surface is opposite with described first surface or continuous.
90. as the described method of claim 89, wherein, the individual layer by a plurality of second materials of sequential aggradation forms second material layer on first material layer, one of individual layer of described second material is deposited on the surface that is deposited on first material layer on the second surface.
91. method as claimed in claim 51, wherein, underlayer temperature is about 500 ℃ or lower when forming first material layer.
92. method as claimed in claim 51, wherein, underlayer temperature is about 300 ℃ or lower when forming first material layer.
93. method as claimed in claim 51, wherein, underlayer temperature is about 200 ℃ or lower when forming first material layer.
94. method as claimed in claim 51, wherein, underlayer temperature is about 150 ℃ or lower when forming first material layer.
95. method as claimed in claim 51, wherein, underlayer temperature is about 80 ℃ or lower when forming first material layer.
96. method as claimed in claim 51, wherein, described polymkeric substance is a thermosetting polymer.
97. goods as claimed in claim 51, wherein, described polymkeric substance is the thermoplastic polymer.
98. a method that forms multilayer film on optical module, it comprises:
Individual layer by a plurality of first materials of sequential aggradation forms first material layer, and one of individual layer of described first material is deposited on the first surface of optical module; And
Individual layer by a plurality of second materials of sequential aggradation forms second material layer, and one of individual layer of described second material is deposited on the surface of first material layer,
Wherein multilayer film comprise first material layer and second material layer, and optical module is lens.
99. a method, it comprises:
Use method while deposit film on first and second surfaces of substrate of ald, described first surface is opposite with described second surface.
100. a method, it comprises:
The method of using ald is deposition first material layer on the first surface of optical substrate and second surface simultaneously, and described first surface is opposite with described second surface.
A kind of method, it comprises:
Use method deposit multilayer film on the surface of the substrate that comprises polymkeric substance of ald.
A kind of on substrate film forming method, it comprises:
Individual layer by a plurality of first materials of sequential aggradation is to form first material layer, and one of individual layer of described first material is deposited on the first surface of substrate,
Wherein film comprises described first material layer, and substrate comprises lens.
A kind ofly comprising film forming method on the substrate of curved surface, it comprises:
Individual layer by a plurality of first materials of sequential aggradation is to form first material layer, and one of individual layer of described first material is deposited on the curved surface of substrate,
Wherein film comprises described first material layer.
A kind of on substrate film forming method, it comprises:
Individual layer by a plurality of first materials of sequential aggradation to be forming first material layer, one of individual layer of described first material sequential aggradation on the first surface and second surface of substrate,
Wherein film comprises described first material layer, and first surface is opposite with second surface.
A kind of on substrate film forming method, it comprises:
Individual layer by a plurality of first materials of sequential aggradation to be forming first material layer, one of individual layer of described first material sequential aggradation on the non-coplanar first surface and second surface of substrate,
Wherein film comprises described first material layer, and first surface links to each other with second surface.
A kind of method, it comprises:
Use method deposit multilayer film on the surface of lens of ald.
A kind of method, it comprises:
Use method deposit multilayer film on curved surface or patterned surface of ald.
A kind of optical system, it comprises:
Being used for will be from the photoimaging of the object lens to the picture plane; With
Optical filtering comprises: relative a plurality of layers of lens position are that the light of λ reduces 20% or more approximately in the amount of being assembled as the place, plane in order to make wavelength with respect to the identical optical system that does not have optical filtering,
One of wherein said a plurality of layers are deposited on the first surface of lens.
As the described optical system of claim 108, wherein, described first surface has and is about 2 meters or littler radius-of-curvature.
110., wherein, describedly be about 5cm or nearer as the plane separation lens as the described optical system of claim 108.
111., wherein, describedly be about 1cm or nearer as the plane separation lens as the described optical system of claim 108.
112., wherein, describedly be about 0.5cm or nearer as the plane separation lens as the described optical system of claim 108.
113., also comprise the detector that is positioned place, described picture plane as the described optical system of claim 108.
114. as the described optical system of claim 113, wherein, described detector is charge coupled array or complementary metal oxide semiconductor (CMOS) array.
115. as the described optical system of claim 113, wherein, described optical filtering is arranged on the surface of detector.
116. as the described optical system of claim 113, wherein, described a plurality of layers comprise a plurality of dielectric layers.
117. as the described optical system of claim 108, wherein, described a plurality of layers alternating layer has different refractivity.
118. as the described optical system of claim 108, wherein, described a plurality of layers comprise a plurality of layers on the second surface that is arranged at the lens opposite with first surface.
119. as the described optical system of claim 108, wherein, λ is about 650nm or bigger.
120. as the described optical system of claim 108, wherein, λ is between about 650nm and 1100nm.
121. as the described optical system of claim 108, wherein, it is that the light of λ reduces about 50% or more that described optical filtering makes the wavelength that focuses on as plane place.
122. as the described optical system of claim 108, wherein, it is that the light of λ reduces about 80% or more that described optical filtering makes the wavelength that focuses on as plane place.
123. as the described optical system of claim 108, wherein, it is that the light of λ reduces about 90% or more that described optical filtering makes the wavelength that focuses on as plane place.
124. as the described optical system of claim 108, wherein, it is that the light of λ reduces about 95% or more that described optical filtering makes the wavelength that focuses on as plane place.
125. as the described optical system of claim 108, wherein, also comprise: be used for and will arrive second lens on picture plane from the photoimaging of object, wherein, one of described optical filtering layer is arranged on the surface of second lens.
126. as the described optical system of claim 108, wherein, imaging light have at the first surface place be about 20 the degree or littler maximum divergence.
127. as the described optical system of claim 108, wherein, imaging light have at the first surface place be about 15 the degree or littler maximum divergence.
128. as the described optical system of claim 108, wherein, imaging light have at the first surface place be about 10 the degree or littler maximum divergence.
129. as the described optical system of claim 108, wherein, optical filtering is positioned between described lens and the described picture plane.
130. one kind comprises the digital camera as the described optical system of claim 108.
131. one kind comprises the mobile phone as the described digital camera of claim 130.
132. an optical system, it comprises that wherein, described optical filtering comprises with respect to the optical filtering of lens and picture plane positioning:
Substrate with first and second surfaces, wherein, described first surface is opposite with described second surface; And
Be separately positioned on described first and second lip-deep first and second multilayer film,
Wherein, described first multilayer film are identical with described second multilayer film.
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CN110747449B (en) * 2019-11-19 2021-01-05 哈尔滨工业大学 A kind of preparation method of self-cleaning hydrophobic film layer for electronic screen
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