Method for depositing layers on a glass substrate by means of low-pressure pecvd

{
  "publication_number": "US2014099451A1",
  "country": "US",
  "kind": "A1",
  "title": "Method for depositing layers on a glass substrate by means of low-pressure pecvd",
  "abstract": "The invention relates to a method for producing metal or semiconductor oxide, nitride or oxynitride films on a substrate, by means of the PECVD method, including the steps that involve: (i) having a low-pressure PECVD device including at least one plasma source that includes at least one electrode connected to an AC, DC, or drawn DC generator for depositing said films on the substrate; and (ii) applying electrical power to the plasma source and applying, on the substrate, an oxide film gas precursor made of metal or semiconductor nitrides or oxynitrides and a reactive gas made of oxygen, oxygen derivatives, or nitrogen derivatives. The invention also relates to metal or semiconductor oxide, nitride, or oxynitride films obtained by the method.",
  "claims": [
    "1. A process for the production of films of oxides, of nitrides or of oxynitrides of metals or semiconductors on a substrate by the Plasma Enhanced Chemical Vapor Deposition (PECVD) method, comprising the stages: a) providing a low-pressure PECVD device comprising at least one linear dual-beam plasma source, which source comprises at least two electrodes connected to an AC or pulsed DC generator, for the deposition of said films on the substrate, b) applying an electrical power between the two electrodes, so that the power density of the plasma is between 5 and 50 W per cm 2 of plasma, and c) applying, to the substrate, a gaseous precursor of films of oxides, of nitrides or of oxynitrides of metals or semiconductors at a flow rate of between 100 and 1000 sccm per linear meter of the plasma source and a reactive gas based on oxygen or on oxygen-comprising derivatives or on nitrogen-comprising derivatives at a flow rate of between 500 and 20 000 sccm per linear meter of the plasma source. 2. A process for the production of films of oxides, of nitrides or of oxynitrides of metals or semiconductors on a substrate by the Plasma Enhanced Chemical Vapor Deposition (PECVD) method, comprising the stages: a) providing a low-pressure PECVD device comprising at least one hollow-cathode plasma source, which source comprises at least one electrode connected to an AC, DC or pulsed DC generator, for the deposition of said films on the substrate, b) applying an electrical power to the plasma source, so that the power density of the plasma is between 15 and 100 kW per meter of plasma, and, c) applying, to the substrate, a gaseous precursor of films of oxides, of nitrides or of oxynitrides of metals or semiconductors at a flow rate of between 100 and 1000 sccm per linear meter of the plasma source and a reactive gas based on oxygen or on oxygen-comprising derivatives or on nitrogen-comprising derivatives at a flow rate of between 500 and 20 000 sccm per linear meter of the plasma source. 3. The process as claimed in claim 1, wherein in stage a), the source of the PECVD device exhibits dimensions of between 250 mm and 4000 mm in length and between 100 and 800 mm in width, providing a power of between 5 kW and 50 kW per linear meter of the plasma source. 4. The process as claimed in claim 1, wherein in stage a), the pressure of the PECVD device is between 0.001 and 0.5 Torr. 5. The process as claimed in claim 1, wherein in stage a), the frequencies of the AC or pulsed DC generator are between 5 and 150 kHz. 6. The process as claimed in claim 1, wherein the reactive gas/gaseous precursor molar ratio is, for the films of M (x) O x/2 type, greater than or equal to (x/2−y)/z, x being the valency of the metal oxide to be obtained, y being the number of oxygen atoms present in the starting precursor and z being the number of oxygen atoms present in the reactive gas. 7. The process as claimed in claim 1, wherein the reactive gas/gaseous precursor molar ratio, for the films of M (x) N x/3 type, is greater than or equal to (x/3−y)/z, x being the valency of the metal nitride to be obtained, y being the number of nitrogen atoms present in the starting precursor and z being the number of nitrogen atoms present in the reactive gas. 8. The process as claimed in claim 1, wherein the ratio of the flow rate of the reactive gas to the flow rate of the gaseous precursor is at least 5. 9. The process as claimed in claim 1, for the production of a glass substrate, further comprising: depositing on and in direct contact with the substrate, an SiO 2 layer, wherein the process is carried out with a power density of greater than 5 W per cm 2 of plasma, the rate of deposition is less than 400 nm·m/min, the pressure of the PECVD device is between 3 and 20 mTorr, with a gaseous precursor of an organosilane derivative and pure oxygen as reactive gas, the ratio of the flow rate of oxygen to the flow rate of the organosilane derivative being greater than 5. 10. The process as claimed in claim 1, further comprising: depositing SiO 2 layers either directly on a glass substrate, or in a stack with other layers in any position, or else as an outermost layer of a stack, for the control of the haze values in stacks intended for solar applications incorporating Low-E layers, said haze values being at least 5%, wherein the process is carried out with a power density of at most 10 W per cm 2 of plasma the flow rate of gaseous precursor of an organosilane derivative is less than 400 sccm per linear meter of plasma source, the ratio of the flow rate of oxygen to the flow rate of the gaseous precursor is greater than 5 and the rate of deposition is less than 400 nm·m/min. 11. The process as claimed in claim 1, further comprising: depositing SiO 2 layers either directly on a glass substrate, or in a stack with other layers in any position, or else as an outermost layer of a stack, for the control of the haze values in stacks intended for solar applications incorporating Low-E layers, said haze values being less than 0.5%, wherein the process is carried out with a power density of at least 5 W per cm 2 of plasma the pressure of the PECVD device is greater than 5 mTorr, the flow rate of gaseous precursor of an organosilane derivative is less than 400 sccm per linear meter of plasma source, the ratio of the flow rate of oxygen to the flow rate of the gaseous precursor is greater than 15 and the rate of deposition is less than 400 nm·m/min. 12. The process as claimed in claim 1, further comprising: depositing layers chosen from the group consisting of SiO 2, ZrO 2 and Al 2 O 3, either directly on a glass substrate or as an outermost layer of a stack, with the aim of conferring scratch-resistant properties on the coated or uncoated substrate, wherein the process is carried out with a power density i-s between 10 and 40 W per cm 2 of plasma, the pressure of the PECVD device is less than 10 mTorr, the flow rate of gaseous precursor of an organosilane derivative is less than 600 sccm per linear meter of plasma source, the ratio of the flow rate of oxygen to the flow rate of the gaseous precursor is greater than 10 and the rate of deposition is less than 400 nm·m/min. 13. The process as claimed in claim 1, further comprising: depositing stacks on a glass substrate exhibiting antireflective (AR) properties, said stack comprising a succession of layers of high refractive indices and having low refractive indices, wherein the process is carried out with a power density between 10 and 40 W per cm 2 of plasma the pressure of the PECVD device is less than 20 mTorr, the flow rate of gaseous precursor of an organosilane derivative is less than 400 sccm per linear meter of plasma source, the ratio of the flow rate of oxygen to the flow rate of the gaseous precursor is greater than 5, the rate of deposition is less than 400 nm·m/min. 14. The process as claimed in claim 1, further comprising: depositing a transparent SiO 2 layer on a glass substrate coated with a Low-E layer, wherein the process is carried out with a power density is greater than 5 W per cm 2 of plasma, the pressure of the PECVD device is less than 20 mTorr, the flow rate of gaseous precursor of an organosilane derivative is less than 400 sccm per linear meter of plasma source, the ratio of the flow rate of oxygen to the flow rate of the gaseous precursor is greater than 5, the rate of deposition is less than 200 nm·m/min. 15. The process as claimed in claim 1, for refreshing the surface of the glass, wherein the process is carried out with a power density of greater than 5 W/cm 2 of plasma, the flow rate of gaseous precursor of an organosilane derivative is less than 200 sccm per linear meter of plasma source, the rate of deposition is less than 200 nm·m/min, the pressure of the PECVD device is less than 15 mTorr, the ratio of the flow rate of oxygen to the flow rate of the gaseous precursor is greater than 5. 16. The process as claimed in claim 2 wherein in stage a), the frequencies of the AC or pulsed DC generator are between 5 and 150 kHz. 17. The process as claimed in claim 2 wherein the reactive gas/gaseous precursor molar ratio is, for the films of M (x) O x/2 type, greater than or equal to (x/2−y)/z, x being the valency of the metal oxide to be obtained, y being the number of oxygen atoms present in the starting precursor and z being the number of oxygen atoms present in the reactive gas. 18. The process as claimed in claim 2 wherein the reactive gas/gaseous precursor molar ratio, for the films of M (x) N x/3 type, is greater than or equal to (x/3−y)/z, x being the valency of the metal nitride to be obtained, y being the number of nitrogen atoms present in the starting precursor and z being the number of nitrogen atoms present in the reactive gas. 19. The process as claimed in claim 2, wherein the ratio of the flow rate of the reactive gas to the flow rate of the gaseous precursor is at least 5. 20. The process as claimed in claim 2, for the production of a glass substrate, further comprising: depositing on and in direct contact with the substrate, an SiO 2 layer, wherein the process is carried out with a power density of greater than 15 kW per meter of plasma, the rate of deposition is less than 400 nm·m/min, the pressure of the PECVD device is between 3 and 20 mTorr, with a gaseous precursor of an organosilane derivative and pure oxygen as reactive gas, the ratio of the flow rate of oxygen to the flow rate of the organosilane derivative is greater than 5. 21. The process as claimed in claim 2, further comprising: depositing SiO 2 layers either directly on a glass substrate, or in a stack with other layers in any position, or else as an outermost layer of a stack, for the control of the haze values in stacks intended for solar applications incorporating Low-E layers, said haze values being at least 5%, wherein the process is carried out with a power density of at most 20 kW per meter of plasma, the flow rate of gaseous precursor of an organosilane derivative is less than 400 sccm per linear meter of plasma source, the ratio of the flow rate of oxygen to the flow rate of the gaseous precursor is greater than 5 and the rate of deposition is less than 400 nm·m/min. 22. The process as claimed in claim 2, further comprising: depositing SiO 2 layers either directly on a glass substrate, or in a stack with other layers in any position, or else as an outermost layer of a stack, for the control of the haze values in stacks intended for solar applications incorporating Low-E layers, said haze values being less than 0.5%, wherein the process is carried out with a power density of at least 15 kW per meter of plasma, the pressure of the PECVD device is greater than 5 mTorr, the flow rate of gaseous precursor of an organosilane derivative is less than 400 sccm per linear meter of plasma source, the ratio of the flow rate of oxygen to the flow rate of the gaseous precursor is greater than 15 and the rate of deposition is less than 400 nm·m/min. 23. The process as claimed in claim 2, further comprising: depositing layers chosen from the group consisting of SiO 2, ZrO 2 and Al 2 O 3, either directly on a glass substrate or as an outermost layer of a stack, with the aim of conferring scratch-resistant properties on the coated or uncoated substrate, wherein the process is carried out with a power density between 20 and 50 kW per meter of plasma, for a hollow-cathode plasma source, the pressure of the PECVD device is less than 10 mTorr, the flow rate of gaseous precursor of an organosilane derivative is less than 600 sccm per linear meter of plasma source, the ratio of the flow rate of oxygen to the flow rate of the gaseous precursor is greater than 10 and the rate of deposition is less than 400 nm·m/min. 24. The process as claimed in claim 2, further comprising: depositing stacks on a glass substrate exhibiting antireflective (AR) properties, said stack comprising a succession of layers of high refractive indices and having low refractive indices, wherein the process is carried out with a power density between 20 and 50 kW per meter of plasma, the pressure of the PECVD device is less than 20 mTorr, the flow rate of gaseous precursor of an organosilane derivative is less than 400 sccm per linear meter of plasma source, the ratio of the flow rate of oxygen to the flow rate of the gaseous precursor is greater than 5, the rate of deposition is less than 400 nm·m/min. 25. The process as claimed in claim 2, further comprising: depositing a transparent SiO 2 layer on a glass substrate coated with a Low-E layer, wherein the process is carried out with a power density greater than 15 kW per meter of plasma, for a hollow-cathode plasma source, the pressure of the PECVD device is less than 20 mTorr, the flow rate of gaseous precursor of an organosilane derivative is less than 400 sccm per linear meter of plasma source, the ratio of the flow rate of oxygen to the flow rate of the gaseous precursor is greater than 5, the rate of deposition is less than 200 nm·m/min. 26. The process as claimed in claim 2, for refreshing the surface of the glass, wherein the process is carried out with a power density of greater than 15 kW per meter of plasma, the flow rate of gaseous precursor of an organosilane derivative is less than 200 sccm per linear meter of plasma source, the rate of deposition is less than 200 nm·m/min, the pressure is less than 15 mTorr, the ratio of the flow rate of oxygen to the flow rate of the gaseous precursor is greater than 5."
  ],
  "cpc": [
    "C03C 17/225",
    "C03C 17/002",
    "C03C 17/245",
    "C03C 17/366",
    "C03C 2217/213",
    "C03C 2217/734",
    "C03C 2217/78",
    "C03C 2218/153",
    "C23C 16/34",
    "C23C 16/40",
    "C23C 16/402",
    "C23C 16/503"
  ],
  "assignees": [
    "MAHIEU STIJN",
    "TIXHON ERIC",
    "VAN STUYVENBERG MARTIN",
    "WIAME HUGUES",
    "AGC GLASS EUROPE"
  ],
  "filing_date": "2012-05-24",
  "publication_date": "2014-04-10",
  "priority_date": "2011-05-25",
  "application_number": "US-201214122111-A",
  "family_id": "46149481",
  "citations": [
    "US2008196664A1",
    "US2010028238A1"
  ]
}