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WO2016018144A1 - Formation a basse temperature de structures de silicium et d'oxyde de silicium - Google Patents

Formation a basse temperature de structures de silicium et d'oxyde de silicium Download PDF

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Publication number
WO2016018144A1
WO2016018144A1 PCT/NL2015/050535 NL2015050535W WO2016018144A1 WO 2016018144 A1 WO2016018144 A1 WO 2016018144A1 NL 2015050535 W NL2015050535 W NL 2015050535W WO 2016018144 A1 WO2016018144 A1 WO 2016018144A1
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poly
silane
silicon
substrate
layer
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PCT/NL2015/050535
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English (en)
Inventor
Ryoichi Ishihara
Miki TRIFUNOVIC
Michiel VAN DER ZWAN
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Technische Universiteit Delft
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Publication of WO2016018144A1 publication Critical patent/WO2016018144A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
    • C23C18/122—Inorganic polymers, e.g. silanes, polysilazanes, polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/16—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers in which all the silicon atoms are connected by linkages other than oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/1225—Deposition of multilayers of inorganic material
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/14—Decomposition by irradiation, e.g. photolysis, particle radiation or by mixed irradiation sources
    • C23C18/143—Radiation by light, e.g. photolysis or pyrolysis
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/60—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which all the silicon atoms are connected by linkages other than oxygen atoms

Definitions

  • Such techniques are used in order to achieve high-throughput, low-cost manufacture of semiconducting devices, including photovoltaic cells and TFT circuitry for displays.
  • Such techniques include the use of inks, i.e. liquid semiconductor, metal and dielectric
  • PEN polyethylene naphthalate
  • PET polyethylene terephthalate
  • the solution is spin-coated onto a substrate and subjected to a drying step in order to remove the solvent.
  • EP1284306 also describes the formation of a silicon dioxde layer by oxidizing a polysilane coating by baking a polysilane coated substrate in an oxygen-environment at a high temperature. Similarly, Tanaka et . al . describe in their article "Solution-processed Si02 films using hydrogenated polysilane based liquid
  • said UV light may be generated by one or more UV light sources, wherein the energy density and/or irradiance of said one or more UV light sources may be selected such that said direct transformation of said first and/or second (poly) silane layer takes place without the need of a substrate heating step for transforming at least part of said first or second (poly) silane into amorphous silicon or amorphous silicon oxide respectively.
  • the term low-temperature process relates to processes wherein no thermal annealing step used before or during the transformation of the (poly) silane into silicon or wherein a thermal annealing step is used in which the annealing temperature is kept below 300 °C,
  • Direct transformation of the (poly) silane into silicon is achieved by exposing the layer to UV laser pulses of a predetermined energy density or to UV LED light of a predetermined irradiance. Because the (poly) silane is directly transformed into crystalline silicon the substrate does not need to be subjected to (substrate) annealing temperatures that are higher than the maximum handling temperature of plastic substrates such as polyamide, PEN or PET. The process does not require high-vacuum conditions and are compatible with roll-to-roll processing.
  • said second (poly) silane may be formed over at least part of said (crystalline) silicon layer.
  • said first (poly) silane may be formed over at least part of said silicon oxide layer.
  • silicon/silicon oxide multilayer structures may be simply formed by the formation of one or more (poly) silane layers and exposing the layers to UV light.
  • transforming said first and/or second (poly) silane layer comprises: exposing said first and/or (poly) silane layer to light from a LED array,
  • liquid silane compound comprising cyclopentasilane (CPS) and/or cyclohexasilane .
  • said (poly) silane layer may be any suitable (poly) silane layer.
  • SiiXjYp a silane compound defined by the general formula SiiXjYp, wherein X represents a hydrogen atom and/or halogen atom and Y represents an boron atom or a phosphorus atom;
  • said (poly) silane layer may be formed on said substrate by applying a substantially pure liquid (poly) silane on said substrate.
  • the substrate may be solid-state substrate including a semiconductor substrate (e.g. silicon) or a glass substrate.
  • the substrate may be a flexible substrate.
  • Suitable materials for flexible substrates may include metals, plastics, paper (cellulose- based materials, woven and non-woven fibre-based materials.
  • the plastic material may comprise polyimide, PEN or PET or derivatives thereof.
  • the (poly) silane is directly transformed into
  • the invention may relate to a method of forming silicon on a substrate comprising: forming a
  • the invention may relate to a method of forming silicon oxide on a substrate comprising: forming a (poly) silane layer over a substrate; transforming said (poly) silane layer into a (crystalline) silicon oxide layer by exposing said second (poly) silane layer to oxygen and/or ozone and to UV light comprising one or more
  • wavelengths within the range between 100 and 450 nm within the range between 100 and 450 nm.
  • the UV light is generated by an UV light source wherein the energy density and/or irradiance of said UV light source is selected such that the transformation of said (poly) silane layer takes place without the need for heating the substrate temperature to temperatures higher than 300 °C, preferably higher 250 °C, more preferably higher 200 °C, even more preferably without heating the temperature of the substrate.
  • the invention may relate to a method of forming a silicon on a substrate comprising: forming a (poly) silane layer over a substrate; transforming said first (poly) silane layer into a (crystalline) silicon layer by exposing said first (poly) silane layer to an UV LED light source, said light source generating one or more wavelengths within the range between 100 and 400 nm, preferably between 200 and 400 nm; wherein said transformation takes places without heating the substrate temperature.
  • said UV LED light source comprises an UV LED array, preferably the light of said a LED array having an irradiance selected between 10 and 1000 mW/cm2, preferably 20 and 800 mW/cm2, more preferably between 40 and 400 mW/cm2.
  • the invention may relate to a method of forming a crystalline silicon layer on flexible cellulose substrate comprising: forming a (poly) silane layer over said substrate; transforming said first (poly) silane layer into a (crystalline) silicon layer by exposing said first (poly) silane layer to light from a (pulsed) laser, preferably, a (pulsed) YAG laser, an argon laser or an excimer laser, the light of said (pulsed) laser having energy density between 20 and 1000 mJ/cm2, preferably 25 and 500 mJ/cm2, more preferably between 50 and 400 mJ/cm2.
  • a (pulsed) laser preferably, a (pulsed) YAG laser, an argon laser or an excimer laser, the light of said (pulsed) laser having energy density between 20 and 1000 mJ/cm2, preferably 25 and 500 mJ/cm2, more preferably between 50 and 400 mJ/cm2.
  • the substrate temperature during said transformation of said (poly) silane layer may be kept below 300 °C, preferably below 250 °C, more preferably below 200 °C, even more preferably at room temperature.
  • the invention may relate to the use of the methods described above, in the manufacturer of a
  • semiconducting device preferably a thin-film transistor, a memory cell or a photovoltaic cell.
  • the invention may relate to the use of the method described above in the manufacturer of an optical coating.
  • FIG. 1A-1C depict a low-temperature process for liquid-based formation of silicon layer according to an embodiment of the invention.
  • Fig. 2A-2C depict AFM measurements and a Raman spectrum of a poly-silicon thin film has have been fabricated using low-temperature processes according to various
  • Fig. 4 depicts a photo of flexible cellulose substrate comprising a polycrystalline silicon coating that is formed using solution-based silicon formation processes according to an embodiment of the invention.
  • Fig. 5A-5C low-temperature solution-based process for the formation of silicon/silicon-oxide structures on a
  • Fig. 7A—7C depicts a low-temperature solution-based process for the formation of silicon nanoparticles according to an embodiment of the invention.
  • Fig. 8A—8F depicts low-temperature solution-based process for the formation of silicon/silicon-oxide structures according to an embodiment of the invention.
  • Fig. 9A—9H depicts low-temperature solution-based process for the formation of silicon/silicon-oxide structures according to another embodiment of the invention.
  • Fig. 10 depicts the use of silicon nanoparticles embedded in the gate insulator of a transistor.
  • the substrate may comprise a flexible substrate material including cellulose-based material and/or a (woven or a non- woven) fibre-based material.
  • the liquid silane may comprise cyclopentasilane (CPS) SisHio.
  • the CPS may be irradiated with UV radiation for a predetermined time.
  • the UV radiation may be used in order to break the CPS rings and to transform at least part of the CPS in (low-order) polysilanes, which are soluble in the CPS.
  • a coating may be formed comprising polysilane or a mixture of polysilane and CPS (a cyclic silane) .
  • a polysilane coating or a mixed polysilane-cyclic silane coating will be referred to as a polysilane coating.
  • the CPS may be irradiated with an UV light having an intensity selected between 1 and 100 mW, preferably between 2 and 50 mW, more preferably between 5 and 20 mW.
  • the coating may be exposed to UV light for a period between 1 and 100 minutes, preferably between 2 and 50 minutes, more preferably between 5 and 40 minutes.
  • the polymerization process transforms the CPS into a polysilane coating or a mixed polysilane-CPS coating that is more viscous and more stable for handing in subsequent
  • the formation of polysilane increases the boiling temperature of the coating so that the coating can be annealed at temperatures higher than the boiling temperature of CPS (around 194 °C) .
  • X is a hydrogen
  • n is preferably an integer of 5 or greater and is more preferably an integer between 5 and 20
  • m is preferably an integer of n, 2n-2, 2n or 2n+l; wherein part of the hydrogen may be replace by a halogen.
  • silane compounds are described in detail in EP1087428, which is hereby incorporated by reference into this application.
  • pentabromocyclopentasilane dodecabromocyclohexasilane, hexabromocyclohexasilane, tetradecabromocycloheptasilane, and heptabromocycloheptasilane .
  • spiro [ 6 , 6 ] tridecasilane substituted silicon compounds in which hydrogen atoms are partly or completely replaced with SiH3 groups or halogen atoms.
  • the liquid silane compound may comprise a cyclic silane, such as cyclopentasilane (CPS) S15H10 and/or cyclohexasilane (CHS) S16H12.
  • CPS cyclopentasilane
  • CHS cyclohexasilane
  • the liquid silane compound may comprise.
  • a substantially pure liquid silane compound or a mixture of at least two substantially pure liquid silane compounds may be used in the formation of a polysilane coating on a substrate.
  • substantially pure may refer to a purity level of a liquid semiconducting precursor of 94%, 96%, 98% or higher than 99%.
  • the polysilane coating may then be transformed into a solid-state silicon layer by exposing the coating to UV light.
  • polysilane coating may be transformed directly, i.e. without any thermal annealing step, in silicon by exposing the polysilane layer to UV radiation for a
  • polysilane coating 108 is exposed to UV light originating from a UV laser system 110.
  • the exposure takes place in an low- oxygen environment (below 10 ppm, more preferably below 1 ppm) or an oxygen-free environment.
  • the UV laser system may
  • the laser light has a wavelength selected within the UV range, preferably between 100 and 450 nm, more preferably between 200 and 400 nm.
  • Examples of such UV laser include but are not limited to excimer lasers, YAG lasers, argon lasers, etc.
  • the UV laser may be configured to transmit short pulses of laser light in the UV spectrum. In an embodiment, the pulse width may be selected between 5 and 500 ns . In another
  • UV laser light pulses may be used to directly transform the polysilane into silicon
  • Fig. 1C depicts a process according to an embodiment of the invention wherein a substrate 102 comprising a
  • each LED or groups of LEDs may be associated with an optical lens and/or
  • the UV LED array may be configured to generate UV light of an irradiance selected between 100 and 800 mW/cm2, preferably 200 and 700 mW/cm2 and the UV LED array may be positioned at a 25-100 mm distance from the substrate surface. Further, the LEDs may be configured to generate UV light in range selected between 100 and 450 nm, preferably between 200 and 400 nm.
  • Fig. 3A-3D show Raman spectra of silicon thin-film that are formed by a exposing a polysilane coating to a single UV laser pulse (XeCl excimer laser, 25 ns pulse width at 308 nm) for increasing energy densities:
  • Fig. 3A shows the result of the exposure of the polysilane coating using a single shot laser pulse of 150 mJ/cm2;
  • Fig. 3B shows the result of the exposure of the polysilane coating using a single shot laser pulse of 200 mJ/cm2;
  • Fig. 3C shows the result of the exposure of the polysilane coating using a single shot laser pulse of 250 mJ/cm2 and
  • Fig. 3D shows the result of the exposure of the polysilane coating using a single shot laser pulse of 300 mJ/cm2.
  • the layers can be effectively transformed into solid-state silicon on the basis of only one or more very short pulses.
  • Such laser pulses may have a pulse width within 10 - 500 ns, hence the transformation of the (poly) silane compounds occurs at a very short time-scale, thus providing a very fast process of forming silicon on the basis of a (poly) silane coating that can be simply applied to a substrate using known solution- based coating and/or printing techniques.
  • transformation implies that there is no need for a separate (intermediate) temperature anneal step for transforming the polysilicon into amorphous silicon as known from prior art processes.
  • Direct transformation of the (poly) silane into silicon has been achieved by exposing the layer to UV laser pulses of a predetermined energy density of to UV LED light of a predetermined irradiance. Because the (poly) silane is directly transformed into crystalline silicon the substrate does not need to be subjected to annealing temperatures that are higher than the maximum handling temperature of flexible substrates such as plastic substrates made from polyamide, PEN and/or PET materials.
  • the UV laser based process allows very fast (single pulse) transformation of the polysilane coating directly into a silicon coating.
  • the UV LED based process allows a simple and cheap way of transforming the polysilane coating directly into a silicon coating. In any way, both processes do not require high-vacuum conditions and are compatible with roll- to-roll processing.
  • the solution-based process described above is used for forming silicon-dioxide (Si02) films or silicon-rich silicon-oxide (SiO x x ⁇ 2) thin-films on a flexible substrate. These processes are described in more detail with reference to Fig. 5A-5C.
  • Fig. 5A depicts a schematic of a low-temperature solution-based process for forming a silicon oxide layer according to an embodiment of the invention.
  • polysilane may be coated onto a substrate 502 in a similar way as described with reference to Fig. 1A.
  • the polysilane coating 504 may be transformed into silicon oxide by exposing the coating to oxygen and/or ozone 505 for a predetermined time as shown in
  • the oxidation time may be selected between 10 and 120 min, preferably between 20 and 60 min.
  • the oxidation process may be accelerated by heating the substrate up to a temperature that is below the maximum handling temperature of the substrate material.
  • the substrate may be heated to a temperature between 100 and 300 °C. In another embodiment, the substrate may be heated up to a temperature selected between 100 and 250 °C . In yet another embodiment, the substrate may be heated up to a temperature selected between 100 and 200 °C.
  • the oxidation process may be accelerated by exposing the polysilane layer to UV light of an UV source 506 during the oxidation step.
  • the polysilane layer may be exposed to UV light.
  • an UV LED system as described with reference to Fig. 1C is used exposing the polysilane layer during the oxidation process.
  • the distance may be selected between 10 and 1000 mm, preferably between 25 and 100 mm.
  • a silicon oxide film may be formed wherein the atomic ration between the oxygen and silicon may be varied between 1 and 2 (i.e. SiO x 1 ⁇ x ⁇ 2) depending on the annealing temperature and/or the intensity of the UV light.
  • Fig. 5A and 5B may be used to form a silicon-rich silicon oxide layer.
  • silicon nanoparticles sometimes also referred to as nanodots
  • Fig. 5C This is schematically shown in Fig. 5C .
  • Exposure of a silicon-rich silicon oxide layer (SiO x x ⁇ 2) to intense UV pulsed laser light from a laser source may induce crystallization of the silicon thereby forming silicon nano-dots in a matrix of Si02.
  • the size of the nano-dots may be controlled by the number of pulses, the pulse width and/or energy density of the UV pules.
  • nanoparticles in the silicon oxide layer may be monitored using spectroscopic ellipsometry as descired in the article by Lee et . al . "optical properties of Si02 /nanocrystalline Si multilayers studied using
  • FIG. 6A-6C depict experimental data associated with the formation of nanoparticles according to an embodiment of the invention.
  • Fig. 6A and 6B depict experimental data associated with the formation of nanoparticles according to an embodiment of the invention.
  • Fig. 6A and 6B depict experimental data associated with the formation of nanoparticles according to an embodiment of the invention.
  • Fig. 6A and 6B depict experimental data associated with the formation of nanoparticles according to an embodiment of the invention.
  • Fig. 6A and 6B depict
  • Fig. 6C depicts a TEM image of the nc-Si dots in the Si02 film.
  • the image is taken with an energy filtered TEM (EFTEM) , in which electrons with an element-specific energy loss are filtered for making the image. Regions containing the specific atoms become bright in the image.
  • the bright spots in TEM image show the presence of nc-Si dots of around 8-10 nm.
  • Nanopart icles embedded in a silicon oxide layer may be used for various applications.
  • a silicon oxide layer comprising nanopart icles may be used as an optical anti- reflection coating or as a storage medium (e.g. a flash memory) .
  • the process depicted in Fig. 5A—5C allows low- temperature formation of such nanopart icles .
  • the formation temperature is lower than the processing temperature of flexible substrates, including plastic substrates such as PET or PEN, cellulose-based material and/or a (woven or a non- woven) fibre-based substrate material.
  • Fig. 7A—7C depicts a low-temperature solution-based process for the formation of silicon nanopart icles according to another embodiment of the invention.
  • Fig. 7A depicts the formation of polysilane coating 704 on a substrate 702 using e.g. a doctor-blade 703 (similar to the process described with reference to Fig. 1A) .
  • the thickness of the polysilane coating may have a reduced thickness
  • the thin polysilane coating is exposed for a predetermined time to UV light (Fig. 7B) originating from an UV source 706.
  • the UV source may be laser of a LED array as described with reference to Fig. IB and 1C.
  • isolated crystalline silicon nanopart icles 708 may formed during the UV exposure as shown in Fig. 7C.
  • the size of the particles and the nanoparticle density may be controlled by the thickness of the polysilane layer and the energy density of the UV laser pulses or the irradiance of the UV LED array. This way nanopart icles of 5 to 50 nm may be formed on a substrate without the need of elevated substrate temperatures.
  • Fig. 8A—8F depicts low-temperature solution-based process for the formation of silicon/silicon-oxide structures according to an embodiment of the invention. The solution- based low temperature process may be used to fabricate silicon - silicon oxide multi-layer structure.
  • FIGS. 8A—8C show the formation of a first (poly) silicon layer 808 on a substrate 802 by coating a polysilane 804 on the substrate using e.g. a doctor blade 803 in order to form a first polysilane layer and exposing the polysilane layer to UV light 806 (similar to the solution-based low temperature process described with
  • a silicon oxide layer 810 may be formed over the silicon layer by coating a polysilane 807 over the first (poly) silicon layer in order to form a second polysilane layer 809.
  • the second polysilane layer is than transformed into a silicon oxide layer by exposing the second polysilane layer to oxygen and/or ozone 814 and, optionally, to UV light 812.
  • the silicon oxide layer may be realized in a similar way as the process described with reference to Fig. 5A-5C .
  • Fig. 8F depicts a further process step in case the silicon oxide layer is formed as a silicon-rich silicon oxide layer 811.
  • silicon nanoparticles 818 may be formed in the silicon oxide layer by exposing the layer to UV light 816 in a similar way as described with reference to Fig. 5C. This way, silicon - silicon oxide multilayers may be formed using a solution-based process that does not require elevated substrate temperatures.
  • nanopart icles may be formed on the silicon - silicon oxide structure in a similar way as
  • a third thin polysilane layer may be formed over the first silicon oxide layer by coating a polysilane 916 over the first silicon oxide layer (Fig. 9E) .
  • the third thin polysilane layer 918 may be exposed to UV light in order to form silicon nanopart icles 922 on top of the first silicon oxide layer 910 (Fig. 9F and 9G) .
  • a second silicon oxide layer 924 may be formed over the silicon nanopart icles so that the nanopart icles are located (embedded) between the first and second silicon oxide layers.
  • the process steps may be repeated in any order in order to realize silicon - silicon oxide multilayer structures using a solution-based low-temperature fabrication technique.
  • Fig. 10 depicts the use of silicon nanopart icles embedded in the gate insulator of a transistor.
  • Fig. 10 depicts the cross-section of at least part of a transistor structure 1000 on a substrate.
  • the substrate may comprise flexible (plastic) substrate 1002 that is covered with silicon oxide layer 1004.
  • the transistor structure may further comprise a polysilicon layer 1006. At least part of the polysilicon layer is covered by a silicon oxide layer 1008 that serves as an insulating layer for the gate metallization 1010. Parts of the polysilicon layer may be doped in order to form source and drain regions 1012i,2.
  • the silicon oxide layer may comprise silicon nano-dots 1014 that serve as a charge trapping media which causes a shift of the threshold voltage of the transistor and which may provide the function of the flash memory.
  • the transistor structure may be realized on the basis of the solution-based low-temperature processes
  • any feature described in relation to any one embodiment may be used alone, or in combination with other features described, and may also be used in combination with one or more features of any other of the embodiments, or any combination of any other of the embodiments.
  • the invention is not limited to the embodiments described above, which may be varied within the scope of the accompanying claims.
  • different coating and/or printing techniques may be used to apply a polysilane layer onto a substrate.
  • Exemplary printing techniques that may be used with the invention include gravure printing, screen printing, flexographic/letterpress printing and/or offset printing.
  • exemplary coating techniques that may be used include slot die coating, roller coating, dip coating, air knife coating, etc.
  • other (flexible) substrates than plastic substrates may be used as a support substrate including metallic, fibre-type (woven or non-woven) sheets, etc .

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Abstract

La présente invention concerne un procédé pour la formation à basse température d'une structure de silicium/oxyde de silicium sur un substrat, le procédé comprenant les suivantes: la formation d'une première couche de (poly)silane sur au moins une partie d'un substrat; la transformation directe de ladite première couche de (poly) silane en une couche de silicium (cristalline) en exposant ladite première couche de (poly)silane à un rayonnement UV comprenant une ou plusieurs longueurs d'onde dans la plage comprise entre 100 et 450 nm; la formation d'une seconde couche de (poly)silane sur au moins une partie dudit substrat; et, la transformation directe de ladite deuxième de (poly)silane couche en une couche d'oxyde de silicium en exposant ladite seconde couche de (poly)silane à l'oxygène et/ou à l'ozone et à la lumière UV comprenant une ou plusieurs longueurs d'onde dans la plage comprise entre 100 et 450nm.
PCT/NL2015/050535 2014-07-31 2015-07-22 Formation a basse temperature de structures de silicium et d'oxyde de silicium WO2016018144A1 (fr)

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