WO2012141908A1 - Dépôt à basse température de films d'oxyde de silicium - Google Patents

Dépôt à basse température de films d'oxyde de silicium Download PDF

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Publication number
WO2012141908A1
WO2012141908A1 PCT/US2012/031122 US2012031122W WO2012141908A1 WO 2012141908 A1 WO2012141908 A1 WO 2012141908A1 US 2012031122 W US2012031122 W US 2012031122W WO 2012141908 A1 WO2012141908 A1 WO 2012141908A1
Authority
WO
WIPO (PCT)
Prior art keywords
wafer
silicon oxide
oxide film
deposition
silicon
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/US2012/031122
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English (en)
Other versions
WO2012141908A8 (fr
Inventor
Curtis Dove
Baljit Singh
Eduard Gil Paran TESNADO
Mehdi Balooch
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Asia Union Electronic Chemical Corp
Original Assignee
Asia Union Electronic Chemical Corp
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 Asia Union Electronic Chemical Corp filed Critical Asia Union Electronic Chemical Corp
Priority to EP12770650.5A priority Critical patent/EP2697826A4/fr
Priority to SG2013074265A priority patent/SG194085A1/en
Publication of WO2012141908A1 publication Critical patent/WO2012141908A1/fr
Publication of WO2012141908A8 publication Critical patent/WO2012141908A8/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P14/00—Formation of materials, e.g. in the shape of layers or pillars
    • H10P14/60—Formation of materials, e.g. in the shape of layers or pillars of insulating materials
    • H10P14/63—Formation of materials, e.g. in the shape of layers or pillars of insulating materials characterised by the formation processes
    • H10P14/6302—Non-deposition formation processes
    • H10P14/6304—Formation by oxidation, e.g. oxidation of the substrate
    • H10P14/6306—Formation by oxidation, e.g. oxidation of the substrate of the semiconductor materials
    • H10P14/6308—Formation by oxidation, e.g. oxidation of the substrate of the semiconductor materials of Group IV semiconductors
    • H10P14/6309—Formation by oxidation, e.g. oxidation of the substrate of the semiconductor materials of Group IV semiconductors of silicon in uncombined form, i.e. pure silicon
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F71/00—Manufacture or treatment of devices covered by this subclass
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F77/00—Constructional details of devices covered by this subclass
    • H10F77/30—Coatings
    • H10F77/306—Coatings for devices having potential barriers
    • H10F77/311—Coatings for devices having potential barriers for photovoltaic cells
    • H10F77/315—Coatings for devices having potential barriers for photovoltaic cells the coatings being antireflective or having enhancing optical properties
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy

Definitions

  • the present invention relates to methods of depositing silicon oxide films at low temperature using wet chemistry techniques.
  • Silicon oxide films are deposited onto silicon surfaces for use in many applications, including as masking layers for semiconductor manufacturing and as anti- reflective coatings for solar cells.
  • CVD chemical vapor deposition
  • CVD processes form the oxide film by exposing the substrate to one or more volatile precursors that react with or decompose onto the substrate surface to produce the desired oxide film.
  • the CVD processes in use differ in how the chemical reactions are initiated (e.g. activation process) and by the process conditions employed.
  • atmospheric pressure CVD APCVD
  • UHCVD ultrahigh vacuum CVD
  • PECVD plasma enhanced CVD
  • ACVD atomic layer CVD
  • Silicon dioxide (Si0 2 ) may be deposited using a CVD technique, by using any one of several source gas precursor combinations.
  • One such combination uses silane and oxygen according to the following reaction formula.
  • a second combination uses oxygen dichloro silane (SiCl 2 H 2 ) and nitrous oxide (N 2 0) according to the following reaction formula. SiCl 2 H 2 + 2N 2 0 -> Si0 2 + 2N 2 + 2HC1
  • TEOS tetraethylorthosilicate
  • source gas depends on the thermal stability of the substrate.
  • silane deposits between 300°C and 500°C
  • the known oxide deposition processes have several disadvantages. These processes require high temperatures and vacuum processing before introduction of the precursor gases, particularly those that are hazardous. Further, the deposition equipment is expensive, has a relatively low wafer throughput, requires frequent cleaning and maintenance and demands highly trained operators. As a result, deposition of silicon oxide films demands substantial capital and operating expense, which increases overall device cost, for example the cost for creating anti-reflective coatings in the photovoltaic industry. Also, backside contact printing, with aluminum or aluminum/gold, is normally performed after the deposition of the oxide, and therefore requires higher temperatures for diffusion of the contacts and reduction in proper contact which could interfere with the overall efficiency of the device.
  • the present invention provides low temperature methods of depositing silicon oxide films using wet chemistry.
  • Figure 1 is a graph showing the reflectance of p-type textured silicon wafers following processing according to the present invention.
  • Figure 2 is a graph showing the reflectance textured silicon wafers doped with phosphor following processing according to the present invention.
  • Figure 3 is a graph showing the reflectance of textured multi-crystalline silicon wafers following processing according to the present invention
  • the present provides methods of depositing silicon oxide films at low temperature using wet chemistry techniques.
  • a wet chemistry mixture of sodium hypo chloride (NaOCl), tetra methyl ammonium hydroxide (TMAH) and hydrated silicate (such as silicic acid) is used for the low temperature oxide deposition.
  • NaOCl is a strong oxidizing agent that ionizes in water to give hypochlorous acid (HOCl) and hypochlorite ions (OCf). If applied to a silicon substrate, the silicon etching rate is low because of the relative lack of availability of OH ions. However, the silicon does react with the hypochlorite ions to form Si0 2 . The process of forming a Si0 2 film using a NaOCl solution alone is a slow process and the film produced is of poor quality. Further this film does not adhere strongly to the silicon substrate. A summary of the reaction sequence is set forth below.
  • TMAH Diluted TMAH (and other hydroxide solutions such as KOH and NaOH) exhibit strong silicon etch rates.
  • the TMAH is reduced to form hydroxyl ions.
  • This is followed by reaction of the hydroxyl ions with silicon atoms at the substrate surface to form oxidized silicates, such as Si (OH) 2 and four electrons are injected from each silicon atom into the conduction band. Therefore, the overall reaction must balance the ions and the electrons.
  • water is reduced to provide more hydroxyl ions which in turn are bonded to the silicates formed in the second step.
  • This reaction produces soluble silicic acid, with hydrogen gas as a by-product.
  • TMAH solution unlike NaOCl, would result in etching of the silicon substrate rather than deposition of an oxide film. This reaction sequence is set forth below.
  • the deposition of an oxide can be accomplished at low temperatures.
  • dilute TMAH or another hydroxide solution having the capability to etch the silicon substrate, with NaOCl that is capable of forming a oxide, and silicate that provides an additional source of silicon for oxidation and deposition, in appropriate amounts, according to the present invention and applying such mixture to a silicon substrate
  • simultaneous etching of the silicon substrate and deposition of oxide can be accomplished at temperatures between 60°C and 90°C.
  • the oxide coatings produced according to the present invention have the proper texture and properties to serve as anti-reflective coatings for solar cells.
  • the thickness of the oxide coating can be adjusted by changing temperature or chemical exposure times to obtain optimal coatings that have low reflectance of visible light. This results in the ability of devices with these coatings to capture the appropriate solar spectrum with increased efficiency of the solar cell.
  • a single crystal Si (100) wafer may be textured using either KOH+IPA, TMAH+IP A or acid solutions such as nitric acid mixed with hydrofluoric acid.
  • the native oxide of the wafer is first removed in a 4% HF solution for several minutes.
  • the wafer is then exposed in accordance with the present invention to a solution of NaOCl, TMAH and extra dissolved Si or added silicic acid. This exposure results in a coating of hydride silica (Polymerized) which when dry heated forms silica having an index of refraction close to Si0 2 ; i.e. about 1.45.
  • Figure 1 shows the reflectance properties of p-type silicon wafers as a function of exposure at 75°C to the solution mixture according to the present invention described above. As can be seen, reflectance is significantly reduced with as little a five minutes exposure, while even better results are achieved with thirteen minutes of exposure. In simulations, the average oxide build-up is 63 nm for five minutes exposure, 93 nm for eight minutes exposure and 120 nm for thirteen minutes exposure.
  • Wafers that were phosphor-diffused using POCl 3 were treated according to the present invention using the solution mixture noted above, i.e. a solution of NaOCl, TMAH and extra dissolved Si or added silicic acid.
  • the results are shown in figure 2.
  • the high doping concentration slowed the deposition rate, the significant reduction in reflectance was still achieved.
  • the rate of deposition on highly phosphor doped substrates was reduced by a factor of up to two compared to deposition rates on low boron doped (p-type) substrates.
  • the present invention of depositing silicon oxide coatings by exposure to wet chemical solutions has several advantages of the CVD deposition techniques used in the prior art.
  • the present invention can be carried out at low temperatures and provides faster deposition rates.
  • the pressent invenition is a simpler process and requires less expensive equipment and fewer utility costs.
  • the present invention does not requires any hazardeous gaseous precursur chemicals.
  • the results of the using the present invention are lower reflectance in the high energy wavelength band of natural light and overall reduced light reflectance when integrated across the light spectrum of 400nm to 1000 run.
  • the present invention is particularly advantageous in solar cell application, where the deposition of oxide anti reflective coating by wet chemistry can be carried out before as well as after contact print film deposition.

Landscapes

  • Photovoltaic Devices (AREA)
  • Formation Of Insulating Films (AREA)
  • Surface Treatment Of Glass (AREA)
  • Paints Or Removers (AREA)

Abstract

La présente invention concerne le dépôt de films d'oxyde de silicium à basse température en utilisant des techniques chimiques par voie humide. La solution chimique par voie humide peut être un mélange d'hypochlorure de sodium (NaOCl), d'hydroxyde de tétra-méthyl-ammonium (TMAH) et de silicate hydraté, tel que de l'acide silicique. Les films d'oxyde de silicium résultants fournissent d'excellents revêtements anti-réfléchissants pour des cellules solaires et analogues.
PCT/US2012/031122 2011-04-12 2012-03-29 Dépôt à basse température de films d'oxyde de silicium Ceased WO2012141908A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP12770650.5A EP2697826A4 (fr) 2011-04-12 2012-03-29 Dépôt à basse température de films d'oxyde de silicium
SG2013074265A SG194085A1 (en) 2011-04-12 2012-03-29 Low temperature deposition of silicon oxide films

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US201161474415P 2011-04-12 2011-04-12
US61/474,415 2011-04-12

Publications (2)

Publication Number Publication Date
WO2012141908A1 true WO2012141908A1 (fr) 2012-10-18
WO2012141908A8 WO2012141908A8 (fr) 2012-11-22

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Application Number Title Priority Date Filing Date
PCT/US2012/031122 Ceased WO2012141908A1 (fr) 2011-04-12 2012-03-29 Dépôt à basse température de films d'oxyde de silicium

Country Status (4)

Country Link
EP (1) EP2697826A4 (fr)
SG (1) SG194085A1 (fr)
TW (1) TW201307610A (fr)
WO (1) WO2012141908A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20160017157A1 (en) * 2013-03-14 2016-01-21 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Coating, method for the production thereof and use thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5445698A (en) * 1992-02-25 1995-08-29 Matsushita Electric Works, Ltd. Method of fabricating an internal composite layer composed of an electrically insulating substrate with a copper layer formed thereon and a film of a coupling agent covering the copper layer for a multilayer circuit board
US20030047111A1 (en) * 2001-09-12 2003-03-13 Kazuma Niume Coating solution for forming transparent silica coating film and method for producing transparent silica coating film
US20090183776A1 (en) * 2008-01-03 2009-07-23 Lg Electronics Inc. Solar cell, method of manufacturing the same, and method of texturing solar cell
US7671001B2 (en) * 2003-10-29 2010-03-02 Mallinckrodt Baker, Inc. Alkaline, post plasma etch/ash residue removers and photoresist stripping compositions containing metal-halide corrosion inhibitors

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5616233A (en) * 1996-05-01 1997-04-01 National Science Council Method for making a fluorinated silicon dioxide layer on silicon substrate by anodic oxidation at room temperature
US20020106865A1 (en) * 2001-02-05 2002-08-08 Tai-Ju Chen Method of forming shallow trench isolation

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5445698A (en) * 1992-02-25 1995-08-29 Matsushita Electric Works, Ltd. Method of fabricating an internal composite layer composed of an electrically insulating substrate with a copper layer formed thereon and a film of a coupling agent covering the copper layer for a multilayer circuit board
US20030047111A1 (en) * 2001-09-12 2003-03-13 Kazuma Niume Coating solution for forming transparent silica coating film and method for producing transparent silica coating film
US7671001B2 (en) * 2003-10-29 2010-03-02 Mallinckrodt Baker, Inc. Alkaline, post plasma etch/ash residue removers and photoresist stripping compositions containing metal-halide corrosion inhibitors
US20090183776A1 (en) * 2008-01-03 2009-07-23 Lg Electronics Inc. Solar cell, method of manufacturing the same, and method of texturing solar cell

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP2697826A4 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20160017157A1 (en) * 2013-03-14 2016-01-21 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Coating, method for the production thereof and use thereof
US10351717B2 (en) * 2013-03-14 2019-07-16 Fraunhofer-Gesellschaft Zur Foerderung Der Angewandten Forschung E.V. Coating, method for the production thereof and use thereof

Also Published As

Publication number Publication date
SG194085A1 (en) 2013-11-29
EP2697826A4 (fr) 2014-10-22
EP2697826A1 (fr) 2014-02-19
WO2012141908A8 (fr) 2012-11-22
TW201307610A (zh) 2013-02-16

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