CN102339905A - Method for manufacturing transparent conductive oxide film glass by using LPCVD (low pressure chemical vapor deposition) technology and taking inorganic salt as precursor - Google Patents
Method for manufacturing transparent conductive oxide film glass by using LPCVD (low pressure chemical vapor deposition) technology and taking inorganic salt as precursor Download PDFInfo
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- CN102339905A CN102339905A CN2011103254646A CN201110325464A CN102339905A CN 102339905 A CN102339905 A CN 102339905A CN 2011103254646 A CN2011103254646 A CN 2011103254646A CN 201110325464 A CN201110325464 A CN 201110325464A CN 102339905 A CN102339905 A CN 102339905A
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- transparent conductive
- conductive oxide
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- 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
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention discloses a method for manufacturing transparent conductive oxide film glass by using an LPCVD (low pressure chemical vapor deposition) technology and taking an inorganic salt as a precursor, comprising the five steps such as glass cleaning, optical detection, film coating, performance detection and formation of a finished product, wherein the film coating step comprises the following procedures: preparing a metal inorganic salt precursor used for preparing a transparent conductive oxide film into a clear saturated water solution; using a bubbler and a carrier gas N2 to load the solution into an LPCVD film-coating chamber; controlling the flow ratio of the inorganic salt precursor to the N2, the pressure and the temperature in the film-coating chamber and the temperature of a glass substrate; and depositing and forming the transparent conductive oxide film on the glass substrate. In the method, the metal inorganic salt is used for replacing an organic precursor so as to manufacture the transparent conductive oxide film glass, thus avoiding pollutions of organisms for a film layer, ensuring good performances of the film-coating glass, being easy to industrialize, and providing a new path for the development of the transparent conductive oxide film glass.
Description
Technical field
The present invention relates to a kind of novel preparation method of transparent conductive oxide film glass, particularly a kind ofly replace traditional metal organic salt, utilize low-pressure chemical vapor deposition technology (LPCVD) to prepare the method for transparent conductive oxide film glass with the inorganic salts predecessor.
Background technology
Transparent conductive oxide film has good photoelectricity, piezoelectricity and air-sensitive character, and its electrochemical stability is high, has purposes widely at aspects such as transparent conductor, fiber waveguide device, high frequency piezoelectric transducer, microsensors.Transparent conductive oxide film glass is the important component part of solar cell especially, particularly is applied to the silicon-based film solar cells aspect, has special advantages.Especially ZnO transparent conductive film glass is because advantages such as it is nontoxic, the source is abundant, low price have caused increasing concern.
At present, the method that is used for preparing transparent conductive oxide film glass mainly comprises magnetron sputtering embrane method, ion beam sputtering deposition method and spraying thermal decomposition method etc., and these preparation methods have its shortcoming.The cost of sputter coating is high, and deposition rate is relatively low; The film performance of spraying thermal decomposition method deposition is relatively poor, and uniformity is not good.The method that is used for preparing transparent conductive oxide film glass at present also has Metalorganic Chemical Vapor Deposition (MOCVD); The predecessor that this method is used is the organic metal alkoxide; With the example that is prepared as of ZnO transparent conductive oxide film glass, its predecessor is zinc methide, diethyl zinc or acetic acid acetone zinc etc.In the process of ZnO film deposition, have few part organic precursors and deposit to simultaneously with ZnO and become foreign particle on the target, thereby cause having organic foreign particle in the transparent conductive oxide rete, influence the various characteristicses such as light transmission, weatherability of film.In the electronic product of large-scale production; Characteristic such as require that the technology of preparing of transparent conductive oxide film glass takes into account that deposition rate height, area are big, good uniformity and cost are low; Therefore, a kind of method that replaces organic precursors to prepare transparent conductive oxide film glass with metal inorganic salt of invention is very necessary.
Summary of the invention
The objective of the invention is to want to overcome low, the defectives such as cost is high, generative capacity is low, film performance difference of uniformity that preparation transparent conductive oxide film glass exists in the prior art; A kind of new method for preparing transparent conductive oxide film glass is provided---prepare the method for transparent conductive oxide film glass with inorganic salts predecessor LPCVD technology; Adopt the transparent conductive oxide film glass of this method preparation; Have higher light transmittance and electric conductivity, good weatherability, preparation technology is simple; Cost is low, is easy to realize industrialization.
For realizing that the technical scheme that above-mentioned purpose of the present invention adopts is: a kind of is the method that predecessor LPCVD technology prepares transparent conductive oxide film glass with inorganic salts, it is characterized in that following these steps to carry out:
1, glass cleans: the sheet glass of getting ready is sent to the glass purging system, cleans and oven dry glass through peracid, alkali, washed with de-ionized water technology;
2, optical detection: with the optics detection system glass after cleaning is detected, whether the observation glass surface has residual spot; The glass that is up to the standards is delivered to the LPCVD coating chamber, and the surface has the glass of residual spot need return the glass purging system to clean again;
3, plated film: the metal inorganic salt predecessor that will prepare transparent conductive oxide film is mixed with the clarification saturated aqueous solution, utilizes bubbler and carrier gas N
2Its solution is loaded in the LPCVD coating chamber N commonly used
2Flow is 300-325 SCCM, inorganic salts predecessor and N
2Mol ratio be 0.2-0.3; For prevent that metal inorganic salt from depositing in pipeline before being written into the LPCVD coating chamber; Can its conveyance conduit be heated to 110 ℃, the pressure in the coating chamber is controlled at 100-500mTorr, and the coating chamber temperature is than the high 150-200 of decomposition temperature ℃ of metal inorganic salt; Metal inorganic salt decomposes in the LPCVD coating chamber, and finally on the substrate of glass than low 50-100 ℃ of coating chamber temperature, deposits the generation transparent conductive oxide film;
4, Performance Detection: light transmittance, thickness and the square resistance of measuring transparent conductive oxide film glass with full spectral reflectance film thickness measuring instrument and four point probe square resistance measuring instrument;
5, finished product is processed: will roll off the production line through the transparent conductive oxide film glass that check meets the coated glass standard, pack on request, number, put in storage, obtain final products; The transparent conductive oxide film glass that check is not met the coated glass standard is recycled to the corrosion pond, and sull it is surperficial with watery hydrochloric acid erodes, and realizes the recycling of glass.
Metal inorganic salt predecessor of the present invention is meant Zn
2+, In
3+, Sn
4+In any with
,
,
,
In any salt of forming.
The present invention adopts metal inorganic salt to replace the predecessor of organic salt as preparation transparent conductive oxide film glass, avoided sneaking into of organic impurities in the film, makes prepared film even; Have higher light transmittance and electric conductivity, good weatherability, and inorganic salts are compared low price with organic salt; Safe; Preparation technology is simple, and cost is low, is fit to industrial mass production.
For the LPCVD preparation method, have the following advantages:
1, the film of preparation has excellent step spreadability and uniformity;
2, the dynamic change dependence to gas flow in the film preparation process is low;
3, the formation time of particulate is shorter in the gas-phase reaction;
4, defect density is low, pollutes and lacks, and productive rate is high.
The present invention can obtain the transparent conductive oxide film glass of different materials and performance through the appropriate change technological parameter.Main technologic parameters comprises base reservoir temperature, flow rate of reactive gas, ratio and operating pressure etc.Wherein the flow of gas has determined the uniformity of large-area coating film, and the flow of gas increases, and the speed of growth of rete is accelerated, and the rete of identical plated film time deposition thickens, and the increase of the crystallite dimension of film material, and side's resistance diminishes, and light transmittance reduces.When the pressure of coating chamber increased, the degree of crystallinity of rete reduced, and side's resistance increases.The temperature and the gas pressure of substrate have determined deposition rate, and base reservoir temperature is high, and deposition rate is fast, and the film material crystallite dimension increases, and side's resistance reduces.In sum; Prepare transparent conductive oxide film glass according to method of the present invention; Can control more accurately its side's resistance, thickness and light transmittance, and manufacture craft is simpler, cost is low; Be easy to realize industrialization, for the industrialization of transparent conductive metal sull glass provides a kind of new approaches.
Embodiment
Through specific embodiment the present invention is described in further detail below, yet said embodiment should not explain with the mode of restriction.
With with Zn (NO
3)
2The method for preparing ZnO transparent conductive oxide film glass for predecessor LPCVD technology is that example specifies as follows:
1, the sheet glass of getting ready is sent to the glass purging system, the KOH aqueous slkali level of employing 5% is scrubbed, and uses high pressure de-ionized water and the common deionized water alternately washing of pressure as 3.5MPa then, with the mode that air knife is dry glass is carried out drying.The air knife drying is a kind of glass drying mode commonly used, it is advantageous that and both can quicken to remove moisture film, makes glass remain on low-temperature condition simultaneously, has reduced precipitation effect, makes the formed point of material on glass or the bar shaped marking drop to minimum point.
2, the glass after cleaning is carried out optical detection, whether the observation glass surface has residual spot, and after the assay was approved clean glass is sent in the LPCVD coating chamber, need return purging system again if any residual spot and clean.
3, with Zn (NO
3)
2The powder saturated aqueous solution that is mixed with transparent clarification soluble in water uses bubbler and carrier gas N
2Its aqueous solution is loaded in the LPCVD coating chamber N
2Flow be 310 SCCM, Zn (NO
3)
2With N
2Mol ratio be 0.2.The pipeline of input predecessor is heated to 110 ℃, prevents Zn (NO
3)
2Before being written into the LPCVD coating chamber, in pipeline, deposit.Pressure limit in the coating chamber is 400mTorr, and reaction temperature is 500 ℃ of (Zn (NO
3)
2Decomposition temperature be 350 ℃), glass substrate is heated to 450 ℃, forms 50 ℃ temperature gradient with temperature in the coating chamber, so that the deposition of ZnO film on glass substrate.Zn (NO
3)
2In coating chamber, decompose, the reaction shown in reaction equation (1) has taken place, finally deposition generates the ZnO transparent conductive oxide film on glass substrate, and produces NO simultaneously
2And O
2Accessory substance is discharged with waste gas.
The preparation doped with Al
2O
3ZnO transparent conductive oxide film glass (AZO), can be in pre-reaction material the compound of doped with Al, like Al (NO
3)
3, Al
2(CO
3)
3, Al (OH)
3Deng, these compound decomposes generate Al
2O
3, Al is mixed in final acquisition
2O
3ZnO transparent conductive oxide film glass, the reaction that alloy takes place is shown in chemical equation (2)-(4).Doping can be added according to the demands of different to product, and doping commonly used is 1.5-5 wt.%, and wherein 2wt.% is the optimum doping value.Al
2O
3Doping can make in the film displacement that produces impurity, produce impurity energy level, carrier concentration increases, move to short wavelength's direction on the optical absorption limit of film.But along with Al
2O
3Continuation increase (>15 wt.%), Al
3+Can cause the distortion of lattice of film, Al
3+Accumulate in the crystal boundary place, become the obstacle of free electron migration, film resiativity increases, and side's resistance increases.
······（3）
Preparation doping Ga
2O
3ZnO transparent conductive oxide film glass (GZO), the same Al of principle
2O
3The doping of material, Ga (NO mixes in pre-reaction material
3)
3, Ga
2(CO
3)
3, Ga (OH)
3Deng the compound of Ga, these compound decomposes generate Ga
2O
3, finally obtain doping Ga
2O
3ZnO transparent conductive oxide film glass, optimum doping amount is 10wt.%, the reaction of generation is shown in equation (5)-(7):
4, after plated film is accomplished, the light transmittance of online testing transparent conductive oxide film glass, thickness and side's resistance.The thickness of film and the light transmission of glass are measured by full spectral reflectance film thickness measuring instrument, and side's resistance of transparent conductive oxide film glass is measured by four point probe square resistance measuring instrument.
5, the transparent conducting ZnO film glass that check is met the coated glass standard rolls off the production line, and packs on request, numbers, puts in storage, obtains final products.Check is not met the product of coated glass standard, be positioned in the corrosion pond and erode, realize the recycling of glass with the watery hydrochloric acid ZnO film that it is surperficial.
Be that predecessor LPCVD method prepares in the process of transparent conductive oxide film glass with the metal inorganic salt, can be with Zn (NO
3)
2Material changes Zn into
2+, In
3+Or Sn
4+In any cation with
,
,
,
In the salt formed of any anion, prepare the transparent conductive oxide film material of different materials with this.
Below again with Sn (SO
4)
2Or In (OH)
3Be predecessor LPCVD technology preparation SnO
2Or In
2O
3The method of transparent conductive oxide film glass further specifies preparation method of the present invention because except that above-mentioned step 3, other each steps all with Zn (NO
3)
2The method that prepare ZnO transparent conductive oxide film glass for predecessor LPCVD technology is identical, therefore below to Sn (SO
4)
2And In (OH)
3Be predecessor LPCVD technology preparation SnO
2Or In
2O
3The step 3 of the method for transparent conductive oxide film glass describes, and other each step no longer repeats.
With Sn (SO
4)
2Be predecessor LPCVD technology preparation SnO
2The method of transparent conductive film glass, its step 3 is: with Sn (SO
4)
2The powder clarification saturated aqueous solution that is mixed with soluble in water utilizes bubbler and carrier gas N
2It is loaded in the LPCVD coating chamber N
2Flow be 300 SCCM, Sn (SO
4)
2With N
2Mol ratio be 0.25.The pipeline of input predecessor is heated to 110 ℃, prevents Sn (SO
4)
2Before being written into the LPCVD coating chamber, in pipeline, deposit.Pressure in the coating chamber is 100mTorr, and reaction temperature is 540 ℃ of (Sn (SO
4)
2Decomposition temperature be 360 ℃), glass substrate is heated to 440 ℃, forms 100 ℃ temperature gradient with reaction temperature, is convenient to SnO
2Depositing of thin film.Sn (SO
4)
2In the LPCVD coating chamber, decompose, the reaction shown in reaction equation (8) has taken place, finally deposition generates SnO on glass substrate
2Film, and generate SO
2And O
2Accessory substance is discharged with waste gas.
With In (OH)
3Be predecessor LPCVD technology preparation In
2O
3The method of transparent conductive film glass, its step 3 is: with In (OH)
3The powder clarification saturated aqueous solution that is mixed with soluble in water utilizes bubbler and carrier gas N
2It is loaded in the LPCVD coating chamber N
2Flow be 325 SCCM, In (OH)
3With N
2Mol ratio be 0.3.The pipeline of input predecessor is heated to 110 ℃, prevents In (OH)
3Before being written into the LPCVD coating chamber, in pipeline, deposit.Pressure limit in the LPCVD coating chamber is controlled at 500mTorr, and is anti-
Answering temperature is 350 ℃ of (In (OH)
3Decomposition temperature be 150 ℃), glass substrate is heated to 280 ℃, forms 70 ℃ temperature gradient with reaction temperature, is convenient to In
2O
3Depositing of thin film.In (OH)
3In the LPCVD coating chamber, decompose, the reaction shown in reaction equation (9) has taken place, finally deposition generates In on glass substrate
2O
3Film, and generate H
2The O accessory substance is discharged with waste gas.
The preparation doped with Al
2O
3Or Ga
2O
3SnO
2Or In
2O
3The method of transparent conductive oxide film glass and preparation doped with Al
2O
3Or Ga
2O
3The method of ZnO transparent conductive oxide film glass identical, its doping scope commonly used is between 1.5-10 wt.%, concrete doping requires to confirm according to properties of product.Reacting of alloy is identical with equation (2)-(7), does not here do and gives unnecessary details.
In coating process, inorganic salts predecessor and N
2Flow or mol ratio increase, the speed of growth of rete is accelerated, the rete of identical plated film time deposition thickens, and the metal oxide film material crystallite dimension that generates increases, side's resistance diminishes, light transmittance reduces.When LPCVD coating chamber pressure increased, the degree of crystallinity of metal oxide reduced, and side's resistance increases.The temperature of substrate and gas pressure have determined the deposition rate of oxide, and base reservoir temperature is high, and deposition rate is fast, and the metal oxide crystallite dimension increases, and side's resistance reduces.Therefore, through repeatedly experiment, the present invention has drawn N
2Flow is 300-325 SCCM, inorganic salts predecessor and N
2Mol ratio be that pressure in 0.2-0.3, the coating chamber is controlled at 100-500mTorr, coating chamber temperature than the high 150-200 of decomposition temperature ℃ of metal inorganic salt, the temperature best scope of application lower 50-100 ℃ than coating chamber temperature of substrate of glass.
Equipment such as described LPCVD coating chamber, bubbler, glass purging system, optical detection apparatus, full spectral reflectance film thickness measuring instrument, four point probe square resistance measuring instrument; Be all the preparation and the inspection machine of conventional transparent conductive oxide film glass; Its method for using also is total to knowledge by the one of ordinary skilled in the art, just no longer repeats here.
More than be to explanation of the present invention and non-limiting, based on other execution modes of inventive concept, all within protection scope of the present invention.
Claims (5)
1. one kind is the method that predecessor LPCVD technology prepares transparent conductive oxide film glass with inorganic salts, it is characterized in that following these steps to carry out:
1., glass cleans: the sheet glass of getting ready is sent to the glass purging system cleans, and the glass after will cleaning is dried;
2., optical detection: whether the glass surface that detects after cleaning with the optics detection system has residual spot, and the glass that is up to the standards is delivered to the LPCVD coating chamber;
3., plated film: the metal inorganic salt predecessor that will prepare transparent conductive oxide film is mixed with the clarification saturated aqueous solution, utilizes bubbler and carrier gas N
2Its solution is loaded in the LPCVD coating chamber used N
2Flow is 300-325 SCCM, inorganic salts predecessor and N
2Mol ratio be 0.2-0.3; Pressure in the coating chamber is controlled at 100-500mTorr; The coating chamber temperature is than the high 150-200 of decomposition temperature ℃ of metal inorganic salt; Metal inorganic salt decomposes in the LPCVD coating chamber, and finally on the substrate of glass than low 50-100 ℃ of coating chamber temperature, deposits the generation transparent conductive oxide film;
4., Performance Detection: light transmittance, thickness and the square resistance of measuring transparent conductive oxide film glass with full spectral reflectance film thickness measuring instrument and four point probe square resistance measuring instrument;
5., finished product packing: will roll off the production line through the transparent conductive oxide film glass that check meets the coated glass standard, packing obtains final products on request.
2. described according to claim 1 is the method that predecessor LPCVD technology prepares transparent conductive oxide film glass with inorganic salts, it is characterized in that described metal inorganic salt predecessor is meant Zn
2+, In
3+, Sn
4+In any with
,
,
,
In any salt of forming.
3. described according to claim 1 is the method that predecessor LPCVD technology prepares transparent conductive oxide film glass with inorganic salts; It is characterized in that before metal inorganic salt is written into the LPCVD coating chamber, its conveyance conduit being heated to 110 ℃, prevent that it from depositing in pipeline.
4. described according to claim 1 is the method that predecessor LPCVD technology prepares transparent conductive oxide film glass with inorganic salts; It is characterized in that the transparent conductive oxide film glass that check is not met the coated glass standard is recycled to the corrosion pond; Sull it is surperficial with watery hydrochloric acid erodes, and realizes the recycling of glass.
According to claim 1 or 2 described be the method that predecessor LPCVD technology prepare transparent conductive oxide film glass with inorganic salts, it is characterized in that the compound of in pre-reaction material doped with Al or Ga, prepare doped with Al
2O
3Or Ga
2O
3ZnO, SnO
2Or In
2O
3Transparent conductive oxide film glass.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011103254646A CN102339905B (en) | 2011-10-24 | 2011-10-24 | Method for manufacturing transparent conductive oxide film glass by using LPCVD (low pressure chemical vapor deposition) technology and taking inorganic salt as precursor |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011103254646A CN102339905B (en) | 2011-10-24 | 2011-10-24 | Method for manufacturing transparent conductive oxide film glass by using LPCVD (low pressure chemical vapor deposition) technology and taking inorganic salt as precursor |
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| CN102339905A true CN102339905A (en) | 2012-02-01 |
| CN102339905B CN102339905B (en) | 2013-03-20 |
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|---|---|---|---|
| CN2011103254646A Expired - Fee Related CN102339905B (en) | 2011-10-24 | 2011-10-24 | Method for manufacturing transparent conductive oxide film glass by using LPCVD (low pressure chemical vapor deposition) technology and taking inorganic salt as precursor |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103680990A (en) * | 2013-12-30 | 2014-03-26 | 中国科学院上海硅酸盐研究所 | Method for using alkaline liquor to clean substrate used for preparing dye-sensitized solar cell |
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|---|---|---|---|---|
| US6306216B1 (en) * | 1999-07-15 | 2001-10-23 | Moohan Co., Ltd. | Apparatus for deposition of thin films on wafers through atomic layer epitaxial process |
| CN1868948A (en) * | 2005-05-27 | 2006-11-29 | 北京化工大学 | Preparation method of indium tin oxide precusor size and ITO thin film |
| CN101337773A (en) * | 2008-08-14 | 2009-01-07 | 浙江理工大学 | Method for preparing ITO film with high conductivity |
| CN101380596A (en) * | 2008-02-03 | 2009-03-11 | 大连理工大学 | Supercritical fluid sedimentation method for preparing nano composite material using inorganic salt as predecessor |
-
2011
- 2011-10-24 CN CN2011103254646A patent/CN102339905B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6306216B1 (en) * | 1999-07-15 | 2001-10-23 | Moohan Co., Ltd. | Apparatus for deposition of thin films on wafers through atomic layer epitaxial process |
| CN1868948A (en) * | 2005-05-27 | 2006-11-29 | 北京化工大学 | Preparation method of indium tin oxide precusor size and ITO thin film |
| CN101380596A (en) * | 2008-02-03 | 2009-03-11 | 大连理工大学 | Supercritical fluid sedimentation method for preparing nano composite material using inorganic salt as predecessor |
| CN101337773A (en) * | 2008-08-14 | 2009-01-07 | 浙江理工大学 | Method for preparing ITO film with high conductivity |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103680990A (en) * | 2013-12-30 | 2014-03-26 | 中国科学院上海硅酸盐研究所 | Method for using alkaline liquor to clean substrate used for preparing dye-sensitized solar cell |
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