CN102339905B - 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 PDF

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CN102339905B
CN102339905B CN2011103254646A CN201110325464A CN102339905B CN 102339905 B CN102339905 B CN 102339905B CN 2011103254646 A CN2011103254646 A CN 2011103254646A CN 201110325464 A CN201110325464 A CN 201110325464A CN 102339905 B CN102339905 B CN 102339905B
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glass
transparent conductive
conductive oxide
oxide film
lpcvd
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CN102339905A (en
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臧晓丹
李昌龄
唐维泰
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CHINA SOLAR POWER (YANTAI) Co Ltd
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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

The method for preparing transparent conductive oxide film glass take inorganic salts as predecessor LPCVD technology
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 widely purposes 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 unique advantage.Especially ZnO transparent conductive film glass is because the 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 spray pyrolysis 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 spray pyrolysis method deposition is relatively poor, and uniformity is not good.The method that is used at present preparing transparent conductive oxide film glass 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 the small 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, affect the various characteristicses such as light transmission, weatherability of film.In the electronic product of large-scale production, the characteristic such as require that the technology of preparing of transparent conductive oxide film glass takes into account that deposition rate height, area are large, 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 the defectives such as the uniformity that preparation transparent conductive oxide film glass exists in the prior art is low, cost is high, generative capacity is low, film performance is poor, 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 the 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 method for preparing transparent conductive oxide film glass take inorganic salts as predecessor LPCVD technology is characterized in that following these steps to carry out:
1, glass cleaning: the sheet glass of getting ready is sent to the glass cleaning system, cleans and oven dry glass through peracid, alkali, washed with de-ionized water technique;
2, optical detection: with Systems for optical inspection the 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 cleaning system to re-start cleaning;
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, its conveyance conduit can be heated to 110 ℃, 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 generates transparent conductive oxide film in the substrate of glass deposition than low 50-100 ℃ of coating chamber temperature;
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 measurement instrument;
5, finished product is made: 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 refers to Zn 2+, In 3+, Sn 4+In any with
Figure 2011103254646100002DEST_PATH_IMAGE001
,
Figure 27397DEST_PATH_IMAGE002
,
Figure 2011103254646100002DEST_PATH_IMAGE003
,
Figure 36810DEST_PATH_IMAGE004
In any salt that forms.
The present invention adopts metal inorganic salt to replace organic salt as the predecessor of preparation transparent conductive oxide film glass, avoided sneaking into of organic impurities in the film, make 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 good step coverage 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 by the appropriate change technological parameter.Main technologic parameters comprises flow, ratio and the operating pressure etc. of base reservoir temperature, reacting gas.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 sheet resistance diminishes, and light transmittance reduces.When the pressure of coating chamber increased, the degree of crystallinity of rete reduced, and sheet resistance increases.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 sheet resistance reduces.In sum, prepare transparent conductive oxide film glass according to method of the present invention, can control more accurately its sheet 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
The present invention is described in further detail below by specific embodiment, yet described embodiment should not explain in the mode of restriction.
To use Zn (NO 3) 2For the method for predecessor LPCVD technology making ZnO transparent conductive oxide film glass is that example is described as follows:
1, the sheet glass of getting ready is sent to the glass cleaning system, the KOH aqueous slkali level of employing 5% is scrubbed, and is high pressure de-ionized water and the alternately washing of common deionized water of 3.5MPa with pressure then, in the mode of air knife drying 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 accelerate to remove moisture film, makes simultaneously glass remain on low-temperature condition, 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 to purging system 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.Pipeline heating to 110 ℃ with the input predecessor 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 occured, finally generate the ZnO transparent conductive oxide film in the glass substrate deposition, and produce simultaneously NO 2And O 2Accessory substance is discharged with waste gas.
Figure 2011103254646100002DEST_PATH_IMAGE005
······?（1）
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, such as 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 occurs is shown in chemical equation (2)-(4).Doping can require according to the difference to product to add, 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, the optical absorption edge of film moves to short wavelength's direction.But along with Al 2O 3Continuation increase (〉 15 wt.%), Al 3+Can cause the distortion of lattice of film, Al 3+Be gathered in grain boundaries, become the obstacle of free electron migration, film resiativity increases, and sheet resistance increases.
Figure 303843DEST_PATH_IMAGE006
······（2）
Figure 2011103254646100002DEST_PATH_IMAGE007
······（3）
Figure 440426DEST_PATH_IMAGE008
······（4）
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 the 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):
Figure 2011103254646100002DEST_PATH_IMAGE009
······（5）
Figure 296256DEST_PATH_IMAGE010
······（6）
Figure 2011103254646100002DEST_PATH_IMAGE011
······（7）
4, after plated film is finished, light transmittance, thickness and the sheet resistance of online testing transparent conductive oxide film glass.The thickness of film and the light transmission of glass are measured by full spectral reflectance film thickness measuring instrument, and the sheet resistance of transparent conductive oxide film glass is measured by four point probe Square resistance measurement 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 with the watery hydrochloric acid ZnO film that it is surperficial, realize the recycling of glass.
Preparing in the process of transparent conductive oxide film glass take metal inorganic salt as predecessor LPCVD method, can be with Zn (NO 3) 2Material changes Zn into 2+, In 3+Or Sn 4+In any cation with
Figure 227303DEST_PATH_IMAGE001
,
Figure 981632DEST_PATH_IMAGE002
,
Figure 905595DEST_PATH_IMAGE003
,
Figure 428980DEST_PATH_IMAGE004
In the salt that forms of any anion, prepare the transparent conductive oxide film material of different materials with this.
The below is again with Sn (SO 4) 2Or In (OH) 3For predecessor LPCVD technology prepares SnO 2Or In 2O 3The method of transparent conductive oxide film glass further specifies preparation method of the present invention because except above-mentioned step 3, other each steps all with Zn (NO 3) 2For the method for predecessor LPCVD technology making ZnO transparent conductive oxide film glass is identical, therefore following only to Sn (SO 4) 2And In (OH) 3For predecessor LPCVD technology prepares 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) 2For predecessor LPCVD technology prepares 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.Pipeline heating to 110 ℃ with the input predecessor 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 2The deposition of film.Sn (SO 4) 2In the LPCVD coating chamber, decompose, the reaction shown in reaction equation (8) has occured, finally generate SnO in the glass substrate deposition 2Film, and generate SO 2And O 2Accessory substance is discharged with waste gas.
Figure 858824DEST_PATH_IMAGE012
······?（8）
With In (OH) 3For predecessor LPCVD technology prepares 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.Pipeline heating to 110 ℃ with the input predecessor 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 3The deposition of film.In (OH) 3In the LPCVD coating chamber, decompose, the reaction shown in reaction equation (9) has occured, finally generate In in the glass substrate deposition 2O 3Film, and generate H 2The O accessory substance is discharged with waste gas.
Figure 2011103254646100002DEST_PATH_IMAGE013
······?（9）
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 determine 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, sheet resistance diminishes, light transmittance reduces.When LPCVD coating chamber pressure increased, the degree of crystallinity of metal oxide reduced, and sheet 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 sheet resistance reduces.Therefore, through many experiments, 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.
The equipment such as described LPCVD coating chamber, bubbler, glass cleaning system, optical detection apparatus, full spectral reflectance film thickness measuring instrument, four point probe Square resistance measurement instrument, be all preparation and the inspection machine of conventional transparent conductive oxide film glass, its using method also is that the one of ordinary skilled in the art is in common knowledge, 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 (4)

1. method for preparing transparent conductive oxide film glass take inorganic salts as predecessor LPCVD technology is characterized in that following these steps to carry out:
1., glass cleaning: the sheet glass of getting ready is sent to the glass cleaning system cleans, and the glass after will cleaning is dried;
2., optical detection: whether the glass surface that detects after cleaning with Systems for optical inspection 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 generates transparent conductive oxide film in the substrate of glass deposition than low 50-100 ℃ of coating chamber temperature; Described metal inorganic salt predecessor refers to Zn 2+, In 3+, Sn 4+In any with
Figure 2011103254646100001DEST_PATH_IMAGE001
, ,
Figure 2011103254646100001DEST_PATH_IMAGE003
,
Figure 2011103254646100001DEST_PATH_IMAGE004
In any salt that forms;
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 measurement 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. according to the method for preparing transparent conductive oxide film glass take inorganic salts as predecessor LPCVD technology claimed in claim 1, 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.
3. according to the method for preparing transparent conductive oxide film glass take inorganic salts as predecessor LPCVD technology claimed in claim 1, 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.
4. according to the method for preparing transparent conductive oxide film glass take inorganic salts as predecessor LPCVD technology claimed in claim 1, it is characterized in that the compound of in pre-reaction material doped with Al or Ga, the preparation doped with Al 2O 3Or Ga 2O 3ZnO, SnO 2Or In 2O 3Transparent conductive oxide film glass.
CN2011103254646A 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 Expired - Fee Related CN102339905B (en)

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