WO2005072947A1 - Films de controle de la lumiere solaire constitues d'heterostructures, et procede de fabrication - Google Patents

Films de controle de la lumiere solaire constitues d'heterostructures, et procede de fabrication Download PDF

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Publication number
WO2005072947A1
WO2005072947A1 PCT/US2004/044081 US2004044081W WO2005072947A1 WO 2005072947 A1 WO2005072947 A1 WO 2005072947A1 US 2004044081 W US2004044081 W US 2004044081W WO 2005072947 A1 WO2005072947 A1 WO 2005072947A1
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WO
WIPO (PCT)
Prior art keywords
energy gap
low energy
solar control
control film
doped
Prior art date
Application number
PCT/US2004/044081
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English (en)
Inventor
Roman David Yuryevich Korotkov
Thomas Dudley Culp
David Alan Russo
Jeffery Lee Stricker
Ryan Christopher Smith
Gary Stephen Silverman
Original Assignee
Arkema 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 Arkema Inc. filed Critical Arkema Inc.
Publication of WO2005072947A1 publication Critical patent/WO2005072947A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/3411—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials
    • C03C17/3417—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials all coatings being oxide coatings
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/208—Filters for use with infrared or ultraviolet radiation, e.g. for separating visible light from infrared and/or ultraviolet radiation
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/26—Reflecting filters

Definitions

  • This invention relates .to solar control films, and more particularly to transparent conductive oxide (TCO) coatings having improved reflectivity in the near infrared (NIR) spectrum.
  • TCO transparent conductive oxide
  • the improved reflectivity is achieved by forming the TCO coatings with heterostructures having different band gaps to increase the electron concentration beyond the solubility limit of a given dopant, and thereby decrease or blue shift the plasma wavelength of the coatings.
  • the invention also relate to a method of making TCO solar control films having the above-described properties.
  • the purpose of solar control coatings is to maximize transmittance of visible light while reflecting most infrared and near infrared (NIR) light.
  • NIR near infrared
  • the wavelength above which most photons will be reflected is the "plasma wavelength,” and the closer the plasma wavelength to the visible (blue) side of the NIR spectrum, the more NIR light will be reflected.
  • Typical solar control coatings are composed of multiple Ag/metal oxide stacks with high visible transmittance ⁇ 80% and high near IR reflectance (-70%). These films have plasma wavelengths ⁇ p of ⁇ 0.7 ⁇ m. Most photons with wavelength ⁇ > ⁇ p will be reflected due to the negative real part of the dielectric constant in this region.
  • pyrolytic coatings composed of transparent conductive oxides (TCOs) such as ITO and doped SnO 2 have high transmission in the visible but NIR reflective properties that are lower than those of sputtered film because their plasma wavelengths generally lie in the 1.0 to 1.6 ⁇ m range.
  • the plasma wavelength is inversely proportional to the square root of the electron concentration, an increase in electron concentration results in a decrease in the plasma wavelength.
  • the electron concentration is limited by the solubility limit of the dopant, which in turn is limited by the site density where the dopant substitutes.
  • the theoretical limit for plasma wavelength in conventional coatings made of In 2 O 3 :Sn (ITO), which 21 3 has an electron concentration of 10 cm- is 22 22 3
  • the highest free electron concentration at room 20 3 temperature (RT) is 7x10 cm- (see H.L. Ma et al, Thin Solid Films 298, 151 (1997)), and the theoretical plasma wavelength limit is 1.3 ⁇ m.
  • the present invention overcomes these theoretical limits by depositing variable band gap heterostructures (quantum wells) to increase doping efficiencies, and therefore electron concentrations, in TCO films.
  • quantum confinement (QC) effect of increasing doping concentration in III-V semiconductor heterostructures is well-known, it has not heretofore been used to increase electron concentration in TCO films for the purpose of decreasing the plasma wavelength.
  • TCOs transparent conductive oxides
  • second objective of the invention to provide TCO coatings having high visible transmittance and plasma wavelengths of less than 1 ⁇ m.
  • metal oxide film stacks with sufficient band gap energy difference using atmospheric pressure chemical vapor deposition (APCVD), the film stacks being composed of various metal oxides such as F doped SnO 2 (3.8 eVVZnO (3.4 eV)/F:SnO 2 (3.8 eV).
  • APCVD atmospheric pressure chemical vapor deposition
  • deposition techniques such as sputtering, molecular beam epitaxy (MBE), or laser-assisted deposition (LAD) may be used to deposit the stacks.
  • the film thickness and morphology of each layer in the stack is preferably controlled by varying deposition conditions such as precursor concentration, carrier gas, substrate temperature, and coreactants and accelerants, such as water.
  • Fig. 1 is a schematic energy diagram of a finite quantum well.
  • Fig. 2 is a schematic diagram showing an example of a superlattice used in a preferred embodiment of the present invention.
  • Fig. 3 is a schematic energy diagram of a triangular potential well formed at the interface of two semiconductors.
  • Fig. 1 shows a heterostructure formed by sandwiching one oxide layer 1 with a low band gap (E G] ) between two oxide layers with a higher band gap (E G2 ), E G1 ⁇ E G
  • E G low band gap
  • E G2 higher band gap
  • E G1 ⁇ E G
  • SL superlattice
  • materials I and II are n-type doped up to their respective solubility limits, the electrons from material II will decrease their potential energy and move into material I because of the difference in the band gaps.
  • the total free electron concentration and Fermi energy (E p ) of material I will increase leading to electron levels above the normal solubility limits. If certain conditions exist, then the heterostructures will exhibit quantum confinement
  • QC structures are any structures where quantum confinement is achieved in multi-layer semiconductor heterostructures with different energy gaps and with wells of considerably small size. The size of the well is determined by n concerned. 1 1 12 13 14 3
  • n s 10 , 10 , 10 , and 10 cm- , respectively.
  • QC is characterized by the formation of single/multiple quantum levels within the low band gap semiconductor.
  • the density of sates in 2D structures is narrower than that of 3D materials and the number of quantum levels is related to the well length and height.
  • TCO film heterostructures with different band gaps are deposited, whereby the number of free electrons is increased beyond that permitted by doping solubility limits of the TCO films.
  • One method of forming the heterostructures is by the controlled atmospheric pressure chemical vapor deposition (APCVD) of organometallic reagents. This method can be used to form heterostructures in a variety of metal oxides including, but not limited to, F doped SnO 2 (3.8 eV)/ZnO (3.4 eV)/F:SnO 2 (3.8 eV).
  • APCVD is used to form doped heterostructures with different band gaps of variable well and barrier height.
  • the increase of the electron concentration inside the well, which is greater than the values obtained by individual doping of a given material has the effect of blue shifting the plasma wavelength.
  • quantum confinement inside the coating material is achieved with a small band gap or well, which not only increases electron concentration but also increases electron mobility.
  • a small band gap or well which not only increases electron concentration but also increases electron mobility.
  • Any triangular potential well formed at the interface of two semiconductors will also qualify as a QC structure (see Fig. 3).
  • Modulation doping is characterized by the dopant separation between high and low energy gap materials. For example, in a SnO 2 (3.8 eV)/ZnO (3.4 eV)/SnO 2 structure, the doping with donors is performed at the SnO 2 /ZnO interfaces.
  • Electrons from the wider gap semiconductor (doped SnO 2 ) (EG2) will transfer to the narrower band gap (EGl) semiconductor (undoped/doped ZnO). A positive charged will be created at the interface of the wider gap material and free electrons will fill the levels in triangular potential wells formed at the interface.
  • the average well size should be smaller than de Broglie wavelength. A more preferred size is 2.5 to 8 nm.
  • the well can be composed of any undoped/doped metal oxide with a lower band gap than the doped metal oxide layers.
  • the 14 2 14 2 preferred sheet carrier concentration should be between -0.1x10 cm- and -1x10 cm- . Oxides with similar crystal structures and lattice parameters are most preferred.
  • Example 1 A 2.2 mm thick glass substrate (soda lime silica), two inches square, was heated on a hot block to about 650°C. The substrate was positioned about 25 mm under the center section of a vertical concentric tube coating nozzle. A carrier gas of dry air flowing at a rate of 12.5 liters per minute (1pm) was heated to about 160°C and passed through a hot wall vertical vaporizer. A liquid coating solution containing monobutyltin trichloride (MBTC) and either 5 or 10 wt% trifluoroacetic acid (TFA) was fed to the vaporizer via a syringe pump at a volume flow designed to give a 0.5 mol % concentration in the gas composition.
  • MBTC monobutyltin trichloride
  • TSA trifluoroacetic acid
  • Doping of ZnO can be conducted using fluorine or Al dopants.
  • the second gas mixture was formed by mixing two separate gas streams in a manifold just before the coating nozzle. The water vapor and air were introduced at the top of the nozzle to minimize premature reaction with the zinc precursor.
  • the DEED liquid was fed via a syringe pump to the second vaporizer through which a nitrogen carrier gas was flowing at 160°C at about 10 slpm. The volume flow was designed to give a 0.5 mol % concentration in the carrier gas. Water was fed via syringe pump into a third vaporizer through which an air carrier gas was flowing at about 10 1pm. The vapor concentration was about 3 mols per mol of zinc precursor.
  • the bilayer film stack was immediately overcoated with a TOF film in the same manner as previously described.
  • the resulting TOF/ZnO/TOF film stack had a visible transmission greater 20 3 than 70 %, an electron concentration in the range of 7-10 xlO e/cm and a mobility higher than 2
  • Stacks with exactly the same (rutile) crystal structure include film stacks composed of SnO 2 /MO ⁇ /SnO 2 , where M equals Ti (3.0 eV), V, Cr, Mo and Ru, which can be deposited from readily available, volatile precursors. The properties of the film stack would be similar to those described in Example 1.

Abstract

L'invention concerne des revêtements transparents en oxyde conducteur pour films de contrôle solaire à réflectivité améliorée dans le spectre de l'infrarouge proche, que l'on forme par dépôt d'hétérostructures ayant différentes largeurs de bande interdites. Les hétérostructures augmentent la concentration électronique au-delà de la limite de solubilité d'un dopant donné, et ainsi diminuent ou mettent en déplacement hypsochrome la longueur d'onde plasma des revêtements.
PCT/US2004/044081 2004-01-23 2004-12-31 Films de controle de la lumiere solaire constitues d'heterostructures, et procede de fabrication WO2005072947A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US53873504P 2004-01-23 2004-01-23
US60/538,735 2004-01-23

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Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007130447A2 (fr) * 2006-05-05 2007-11-15 Pilkington Group Limited Procédé de dépôt de revêtements d'oxyde de zinc sur du verre plat
JP2010502832A (ja) * 2006-08-29 2010-01-28 ピルキングトン・グループ・リミテッド 酸化亜鉛被覆物品の作成方法
JP2010502831A (ja) * 2006-08-29 2010-01-28 ピルキングトン・グループ・リミテッド 低抵抗率のドープ酸化亜鉛コーティングを作る方法及び当該方法により形成される物品
EP2343579A1 (fr) 2009-12-23 2011-07-13 Rohm and Haas Company Particules composites pour filtres de bande passante optique
WO2013052927A2 (fr) * 2011-10-07 2013-04-11 Svaya Nanotechnologies, Inc. Film de contrôle solaire à large bande
US8841375B2 (en) 2007-09-27 2014-09-23 Basf Se Isolable and redispersable transition metal nanoparticles their preparation and use as IR absorbers
US9181124B2 (en) 2007-11-02 2015-11-10 Agc Flat Glass North America, Inc. Transparent conductive oxide coating for thin film photovoltaic applications and methods of making the same
US9387505B2 (en) 2012-09-17 2016-07-12 Eastman Chemical Company Methods, materials and apparatus for improving control and efficiency of layer-by-layer processes
US9393589B2 (en) 2011-02-15 2016-07-19 Eastman Chemical Company Methods and materials for functional polyionic species and deposition thereof
US9453949B2 (en) 2014-12-15 2016-09-27 Eastman Chemical Company Electromagnetic energy-absorbing optical product and method for making
US9817166B2 (en) 2014-12-15 2017-11-14 Eastman Chemical Company Electromagnetic energy-absorbing optical product and method for making
US9891357B2 (en) 2014-12-15 2018-02-13 Eastman Chemical Company Electromagnetic energy-absorbing optical product and method for making
US9891347B2 (en) 2014-12-15 2018-02-13 Eastman Chemical Company Electromagnetic energy-absorbing optical product and method for making
US10338287B2 (en) 2017-08-29 2019-07-02 Southwall Technologies Inc. Infrared-rejecting optical products having pigmented coatings
US10613261B2 (en) 2018-04-09 2020-04-07 Southwall Technologies Inc. Selective light-blocking optical products having a neutral reflection
US10627555B2 (en) 2018-04-09 2020-04-21 Southwall Technologies Inc. Selective light-blocking optical products having a neutral reflection
US11747532B2 (en) 2017-09-15 2023-09-05 Southwall Technologies Inc. Laminated optical products and methods of making them

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4975567A (en) * 1989-06-29 1990-12-04 The United States Of America As Represented By The Secretary Of The Navy Multiband photoconductive detector based on layered semiconductor quantum wells
US5952084A (en) * 1996-02-22 1999-09-14 Saint Gobain Vitrage Transparent substrate provided with a thin-film coating
US6238781B1 (en) * 1995-02-23 2001-05-29 Saint-Gobain Vitrage Transparent substrate with antireflection coating

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4975567A (en) * 1989-06-29 1990-12-04 The United States Of America As Represented By The Secretary Of The Navy Multiband photoconductive detector based on layered semiconductor quantum wells
US6238781B1 (en) * 1995-02-23 2001-05-29 Saint-Gobain Vitrage Transparent substrate with antireflection coating
US5952084A (en) * 1996-02-22 1999-09-14 Saint Gobain Vitrage Transparent substrate provided with a thin-film coating

Cited By (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007130447A3 (fr) * 2006-05-05 2008-01-24 Pilkington Group Ltd Procédé de dépôt de revêtements d'oxyde de zinc sur du verre plat
US7670647B2 (en) 2006-05-05 2010-03-02 Pilkington Group Limited Method for depositing zinc oxide coatings on flat glass
WO2007130447A2 (fr) * 2006-05-05 2007-11-15 Pilkington Group Limited Procédé de dépôt de revêtements d'oxyde de zinc sur du verre plat
JP2010502832A (ja) * 2006-08-29 2010-01-28 ピルキングトン・グループ・リミテッド 酸化亜鉛被覆物品の作成方法
JP2010502831A (ja) * 2006-08-29 2010-01-28 ピルキングトン・グループ・リミテッド 低抵抗率のドープ酸化亜鉛コーティングを作る方法及び当該方法により形成される物品
JP2013053066A (ja) * 2006-08-29 2013-03-21 Pilkington Group Ltd 酸化亜鉛被覆物品の作成方法
US8841375B2 (en) 2007-09-27 2014-09-23 Basf Se Isolable and redispersable transition metal nanoparticles their preparation and use as IR absorbers
US9181124B2 (en) 2007-11-02 2015-11-10 Agc Flat Glass North America, Inc. Transparent conductive oxide coating for thin film photovoltaic applications and methods of making the same
EP2343579A1 (fr) 2009-12-23 2011-07-13 Rohm and Haas Company Particules composites pour filtres de bande passante optique
US9551817B2 (en) 2009-12-23 2017-01-24 Rohm And Haas Company Composite particles for optical bandpass filters
US9393589B2 (en) 2011-02-15 2016-07-19 Eastman Chemical Company Methods and materials for functional polyionic species and deposition thereof
WO2013052927A3 (fr) * 2011-10-07 2013-07-18 Svaya Nanotechnologies, Inc. Film de contrôle solaire à large bande
US9395475B2 (en) 2011-10-07 2016-07-19 Eastman Chemical Company Broadband solar control film
WO2013052927A2 (fr) * 2011-10-07 2013-04-11 Svaya Nanotechnologies, Inc. Film de contrôle solaire à large bande
US9387505B2 (en) 2012-09-17 2016-07-12 Eastman Chemical Company Methods, materials and apparatus for improving control and efficiency of layer-by-layer processes
US9453949B2 (en) 2014-12-15 2016-09-27 Eastman Chemical Company Electromagnetic energy-absorbing optical product and method for making
US9817166B2 (en) 2014-12-15 2017-11-14 Eastman Chemical Company Electromagnetic energy-absorbing optical product and method for making
US9891357B2 (en) 2014-12-15 2018-02-13 Eastman Chemical Company Electromagnetic energy-absorbing optical product and method for making
US9891347B2 (en) 2014-12-15 2018-02-13 Eastman Chemical Company Electromagnetic energy-absorbing optical product and method for making
US10338287B2 (en) 2017-08-29 2019-07-02 Southwall Technologies Inc. Infrared-rejecting optical products having pigmented coatings
US11747532B2 (en) 2017-09-15 2023-09-05 Southwall Technologies Inc. Laminated optical products and methods of making them
US10613261B2 (en) 2018-04-09 2020-04-07 Southwall Technologies Inc. Selective light-blocking optical products having a neutral reflection
US10627555B2 (en) 2018-04-09 2020-04-21 Southwall Technologies Inc. Selective light-blocking optical products having a neutral reflection

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