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WO1993016811A1 - Procede de depot d'une couche mince sur un circuit a semi-conducteurs - Google Patents

Procede de depot d'une couche mince sur un circuit a semi-conducteurs Download PDF

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Publication number
WO1993016811A1
WO1993016811A1 PCT/US1993/000259 US9300259W WO9316811A1 WO 1993016811 A1 WO1993016811 A1 WO 1993016811A1 US 9300259 W US9300259 W US 9300259W WO 9316811 A1 WO9316811 A1 WO 9316811A1
Authority
WO
WIPO (PCT)
Prior art keywords
flow
substrate
excited state
metalorganic vapor
state species
Prior art date
Application number
PCT/US1993/000259
Other languages
English (en)
Inventor
Jeff Bullington
Robert V. Ellis
Richard T. Walker
Original Assignee
Radiant Technologies, Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Radiant Technologies, Inc. filed Critical Radiant Technologies, Inc.
Publication of WO1993016811A1 publication Critical patent/WO1993016811A1/fr

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Classifications

    • 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
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/48—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating by irradiation, e.g. photolysis, radiolysis, particle radiation
    • 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
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/40—Oxides
    • C23C16/409—Oxides of the type ABO3 with A representing alkali, alkaline earth metal or lead and B representing a refractory metal, nickel, scandium or a lanthanide
    • 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
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/448—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for generating reactive gas streams, e.g. by evaporation or sublimation of precursor materials
    • C23C16/452—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for generating reactive gas streams, e.g. by evaporation or sublimation of precursor materials by activating reactive gas streams before their introduction into the reaction chamber, e.g. by ionisation or addition of reactive species

Definitions

  • the present invention relates to methods for depositing thin film coatings, and more particularly to depositing ferroelectric thin film coatings onto the surface of substrates that cannot withstand high temperatures.
  • the silicon chip has become a symbol of modern electronics.
  • Semiconductor-based devices dominate the digital electronic world, and new applications of such devices are continually being created. As these applications demand greater optimization, semiconductor devices are developed which are both smaller and faster than their predecessors.
  • a single modern integrated circuit contains a multitude of distinct transistor and other semiconductor devices on a single piece of semiconductor material.
  • capacitance is also dependent upon the material used for manufacturing the capacitor. Therefore, it would be desirable to utilize materials for semiconductor capacitors which would provide larger capacitances than do the materials in present use. It would be yet more desirable to utilize such materials were they capable of further reduction in thickness.
  • ferroelectrics such as lead zirconate titanate (PZT) and lead lanthanum zirconate titanate (PLZT).
  • PZT lead zirconate titanate
  • PLAT lead lanthanum zirconate titanate
  • thin film layers of these ferroelectrics on semiconductor materials could be used as active elements in a variety of thin film electro-optical devices such as optical disks, optical coatings, or optical computing logic.
  • Films must be conformal, which means that the film must fill in surface features. These surface features may vary from tenths of a micron to several microns in depth and lateral extent.
  • the films themselves must have a well controlled stoichiometry, which means that the ratios of the elements comprising the ferroelectric, e.g. lead, zirconium, and titanium , and perhaps lanthanum, must be well controlled.
  • a pure perovskite-phase material must be produced. In addition, this uniformity must be maintained over areas which may exceed areas with 8 inch diameters, and must be maintained while allowing high film growth rates.
  • Prior art methods such as sol-gel or rf and magnetron sputtering may be used for small scale deposition of ferroelectrics, but cannot produce conformal films over large features, and are not capable of producing a uniformly composed film over large areas with a high film growth rate. Hence, these methods appear incapable of meeting the demands of low cost commercial manufacturing of such thin film devices.
  • MOCVD metalorganic chemical vapor deposition
  • the present invention comprises a method for coating the surface of a substrate with a thin film of ferroelectric material.
  • a flow of a metalorganic vapor directed towards the substrate is generated.
  • the metalorganic vapor includes precursor compounds to the ferroelectric material of the coating.
  • a flow of excited state species is generated.
  • the flow of excited state species is directed to intersect the path of the flow of metalorganic vapor at a location displaced from the surface of the substrate. The intersection is chosen such that the metalorganic vapor and excited state species collide and produce a flow of activated metalorganic vapor.
  • the substrate is heated to a predetermined temperature which is chosen to be less than 400° C.
  • the flow of activated metalorganic vapor is directed to collide with the surface of the heated substrate.
  • the metalorganic vapor comprises a combination of tetraethyl lead, zirconium t-butoxide, and titanium iso-propoxide for a PZT layer, and lanthanum 2,2,6,6,-tetramethyl-3,5- heptanedionate, zirconium t-butoxide, and titanium iso-propoxide for a PLZT layer.
  • the flow of ionized particles comprises a flow of ionized helium, and is directed by means of a pressurized gas flow.
  • the step of generating a flow of ionized particles comprises the step of directing a plasma gas flow towards the silicon substrate and through a radio frequency electromagnetic field of sufficient field intensity to ionize the. plasma gas.
  • the method of the present invention may also be used to produce thin film coatings of a variety of other materials to the surface of an integrated circuit device.
  • Figure 1 illustrates a PE-MOCVD reactor in which the preferred implementation of the method of the present invention may be performed.
  • the method of the present invention may be described as a Plasma Enhanced Metalorganic Chemical Vapor Deposition (PE-MOCVD) method. This is an improvement to the MOCVD method described above.
  • PE-MOCVD Plasma Enhanced Metalorganic Chemical Vapor Deposition
  • the excited state species are directed to a location spatially removed from the substrate surface, where the excited state species interact with the metalorganic precursor vapor. It is important to have the interaction at a point removed from the substrate since locating a substrate within the particle flow can lead to serious problems such as film and substrate damage from high energy electron and ion bombardment, lack of control over the chemical environment at the film growth surface, and gas phase particle nucleation from precursors entering the discharge. These problems are avoided by the displacement of the location of the excited state species-precursor interaction from the plasma generation zone.
  • the reactor includes four major sections.
  • the excited state species comprise non- izoned atoms in excited states.
  • the second is a precursor activation chamber 20, in which the excited state species are utilized to activate a flow of precursor vapor to render the precursor vapor more susceptible to successful deposition upon the surface of substrate 32.
  • the third is the film growth chamber, in which the substrate 32 is heated by a heater 36 and is bombarded with activated precursor vapor. The combination of activated precursor vapor with the heated substrate surface yields more effective deposition of film material.
  • a vacuum exhaust system 40 generates a low pressure region which draws residual activated precursor vapor and discharges the vapor. The vacuum thereby produced is essential to the proper flow of gasses within the reactor.
  • a flow of a precursor vapor is generated by precursor vapor injectors 22. This flow is directed towards the substrate 32.
  • the flow can be adjusted by changing the relative positions of precursor vapor injectors 22 and substrate holder 34.
  • Precursor vapor injectors 22 may be moved relative to film growth chamber 30 and substrate holder 34 may be manipulated by moving substrate manipulator 46.
  • secondary activating species may be introduced with the precursor vapor to facilitate activation and film deposition.
  • a flow of ionized particles is produced by discharging a plasma gas into plasma generation chamber 10 by means of plasma gas inlets 12.
  • the plasma gas is set into motion by means of a flow generated by vacuum exhaust system 40, which creates a pressure difference which induces the flow.
  • a radio-frequency electromagnetic field is generated by rf coil 14 which causes the plasma gas to ionize, thereby generating a plasma. This plasma is therefore a flow of ionized particles.
  • the plasma flows towards substrate 32.
  • a buffer gas may be introduced at buffer inlets 16.
  • the buffer gas facilitates plasma transport and activation of the precursor vapor, as described below.
  • the afterglow of the plasma continues to flow into precursor activation zone 20.
  • Precursor activation zone 20 is displaced from plasma generation chamber 10 by a sufficient distance to allow substantially all of the ionized particles in the plasma to decay to excited state species.
  • the afterglow is directed by the vacuum to flow so as to intersect the path of the flow of precursor compound vapor in precursor activation zone 20.
  • Precursor activation zone 20 is displaced from the surface of substrate 32. The two flows intersect such that the precursor vapor and excited state species particles in the plasma afterglow collide.
  • the excited state species particles interact with the precursor vapor, transforming the precursor compound into an "activated" precursor vapor. This process therefore results in the production of a flow of activated precursor vapor.
  • a buffer gas may be introduced at buffer inlets 16.
  • the buffer gas facilitates plasma transport and activation of the precursor vapor.
  • substrate 32 is heated to a predetermined temperature by means of heater 36 and thermocouple 38.
  • this predetermined temperature is chosen to be less than 400° C.
  • the specific temperature chosen is dependent upon the maximum temperature to which the substrate may be heated without damage thereto. Hence, the temperature is dependent upon the substrate material itself.
  • the flow of activated precursor vapor is directed to collide with the surface of substrate 32.
  • the locations of substrate holder 34 and precursor vapor injectors 22 may be adjusted so that the flow is properly directed towards substrate 32, as mentioned above.
  • a thin film of a ferroelectric material is deposited onto a silicon surface.
  • a PZT or a PLZT is to be deposited.
  • the precursor vapor is comprised of a combination of metalorganic compounds, which preferably are tetraethyl lead, zirconium t-butoxide, and titanium iso-propoxide for PZT films and tetraethyl lead, lanthanum 2,2,6,6,-tetramethyl-3,5-heptanedionate, zirconium t- butoxide, and titanium iso-propoxide for PLZT films.
  • Other precursor compounds may be substituted, dependent upon the film material sought to be deposited.
  • the flow of plasma in the preferred implementation comprises a flow of ionized helium.
  • the plasma is generated by passing a 13.56 MHz rf voltage through rf coil 14.
  • the buffer gas is also helium gas.
  • Alternative gasses may be used, as will be obvious to those skilled in the art.
  • the gas pressures at the various locations within the reactor are critical to its operation.
  • the pressure differentials between plasma gas inlets 12, plasma generation zone 18, and precursor activation zone 20 must be such that a continuous gas and plasma flow is achieved, and that precursor vapor does not flow into plasma generation zone 18.
  • the gas pressures are maintained by regulating vacuum exhaust system 40, buffer inlets 16, plasma gas inlets 12 and precursor vapor injectors 22 in a standard feedback control loop.
  • monitoring and control devices (not shown) are utilized in the regulatory feedback loop.
  • a capacitance manometer and a controller are included.
  • Exhaust system 40 would include an exhaust throttle valve.
  • a metering valve may be included on buffer inlets 16.
  • Plasma gas inlets 12 and buffer inlets 16 may have gas flow rates regulated by mass flow controllers.
  • Precursor vapor injectors 22 may be regulated by metered carrier gas flows through heated bubbler tubes or by means of pressure controlled vapor metering valves. The specific regulation devices may be chosen in light of the precursor compounds and plasma gas utilized.

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  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Chemical Vapour Deposition (AREA)

Abstract

Procédé d'application d'une couche mince d'un matériau ferroélectrique sur la surface d'un substrat. Un courant d'une vapeur métallo-organique telle que du plomb tétraéthyle, du t-butoxyde de zirconium et de l'isopropoxyde de titane est dirigé vers le substrat de silicium. Un courant de particules ionisées est également généré lorsqu'on expose un gaz à un champ électromagnétique HF. L'incandescence résiduelle de particules d'une espèce à l'état excité entrecroise la trajectoire du courant de vapeur métallo-organique à un endroit espacé par rapport à la surface du substrat, produisant ainsi un courant de vapeur métallo-organique activée qui se dépose alors sur le substrat chauffé. La figure représente un réacteur de dépôt en phase vapeur par procédé chimique stimulé par plasma, lequel comprend un générateur de plasma (10) dans lequel l'espèce excitée est générée, une chambre d'activation de précurseur (20), la zone de dépôt (32) où se situe le substrat chauffé, et un système d'évacuation (40).
PCT/US1993/000259 1992-02-21 1993-01-13 Procede de depot d'une couche mince sur un circuit a semi-conducteurs WO1993016811A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US83916792A 1992-02-21 1992-02-21
US07/839,167 1992-02-21

Publications (1)

Publication Number Publication Date
WO1993016811A1 true WO1993016811A1 (fr) 1993-09-02

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Application Number Title Priority Date Filing Date
PCT/US1993/000259 WO1993016811A1 (fr) 1992-02-21 1993-01-13 Procede de depot d'une couche mince sur un circuit a semi-conducteurs

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AU (1) AU3582793A (fr)
WO (1) WO1993016811A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2305940A (en) * 1995-10-04 1997-04-23 Hyundai Electronics Ind Method for forming ferroelectric thin film and apparatus therefor
EP1205576A4 (fr) * 2000-03-29 2003-08-20 Seiko Epson Corp Procede de production de ceramique et appareil pour sa production, dispositif a semi-conducteur et dispositif piezo-electrique
WO2006045885A1 (fr) * 2004-10-26 2006-05-04 Asm International N.V. Procede permettant de deposer des films contenant du plomb

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4963390A (en) * 1988-10-05 1990-10-16 The Aerospace Corporation Metallo-organic solution deposition (MOSD) of transparent, crystalline ferroelectric films
US5104690A (en) * 1990-06-06 1992-04-14 Spire Corporation CVD thin film compounds
US5116643A (en) * 1987-06-02 1992-05-26 National Semiconductor Corporation Method for preparing PLZT, PZT and PLT sol-gels and fabricating ferroelectric thin films
US5138520A (en) * 1988-12-27 1992-08-11 Symetrix Corporation Methods and apparatus for material deposition

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5116643A (en) * 1987-06-02 1992-05-26 National Semiconductor Corporation Method for preparing PLZT, PZT and PLT sol-gels and fabricating ferroelectric thin films
US4963390A (en) * 1988-10-05 1990-10-16 The Aerospace Corporation Metallo-organic solution deposition (MOSD) of transparent, crystalline ferroelectric films
US5138520A (en) * 1988-12-27 1992-08-11 Symetrix Corporation Methods and apparatus for material deposition
US5104690A (en) * 1990-06-06 1992-04-14 Spire Corporation CVD thin film compounds

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2305940A (en) * 1995-10-04 1997-04-23 Hyundai Electronics Ind Method for forming ferroelectric thin film and apparatus therefor
GB2305940B (en) * 1995-10-04 2000-03-29 Hyundai Electronics Ind Method for forming ferroelectric thin film
EP1205576A4 (fr) * 2000-03-29 2003-08-20 Seiko Epson Corp Procede de production de ceramique et appareil pour sa production, dispositif a semi-conducteur et dispositif piezo-electrique
US7018676B2 (en) 2000-03-29 2006-03-28 Seiko Epson Corporation Method and device for manufacturing ceramics, semiconductor device and piezoelectric device
WO2006045885A1 (fr) * 2004-10-26 2006-05-04 Asm International N.V. Procede permettant de deposer des films contenant du plomb

Also Published As

Publication number Publication date
AU3582793A (en) 1993-09-13

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