CN1560910A - Photovoltaic semiconductor thin film plating liquid and its preparation method - Google Patents
Photovoltaic semiconductor thin film plating liquid and its preparation method Download PDFInfo
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- CN1560910A CN1560910A CNA2004100167716A CN200410016771A CN1560910A CN 1560910 A CN1560910 A CN 1560910A CN A2004100167716 A CNA2004100167716 A CN A2004100167716A CN 200410016771 A CN200410016771 A CN 200410016771A CN 1560910 A CN1560910 A CN 1560910A
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- cds
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- polyethylene glycol
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Abstract
The invention is a light semi-conductor film plating liquid and the manufacturing method, which is applied to the semi-conductor film technology field grown with liquid phase. The plating liquid is: CdCl2 0.07-5%, NH4NO3 0.1-4%, KOH 1-6%, CS (NH2)2 0.3-15%, polyethylene glycol 0.1-1%, the residue is deioned water it produces even thick CdS film through adding polyethylene glycol. The concrete manufacturing steps are: the base plate is processed with rinsing by acetone and deioned water supersonic, they are dried for backup; the CdCl2, KOH, NH2NO3 liquid and polyethylene glycol are poured into the beaker in the liquid confecting process, uses the KOH to adjust the pH value of the plating liquid to be proper, wait 20 minutes; when the solvent is stable, it is heated to 60-90deg.C, adds in the preprocessed thiourea liquid, after being blended evenly, puts in the base plate vertically, the plating process is carried on; after being deposited, eliminates the CdS particle attaching on the film surface with supersonic rinsing.
Description
Technical field
What the present invention relates to is to be used for liquid growth semiconductor film technique field, particularly a kind of photovoltaic semiconductors film plating bath and preparation method thereof.
Background technology
CdS is as a kind of n N-type semiconductor N (E of medium energy gap
g=2.4eV), caused people's extensive interest at the aspects such as chemical conversion, storage and solar cell of solar energy.Polycrystalline CdS film is applied to CuInSe as window material usually
2And CdTe solar cell.Chemical bath deposition in numerous preparation methods, promptly CBD (Chemical bath deposition) but preparation CdS thin film technique is simple, with low cost with its technology, film forming evenly and advantage such as large tracts of land production received suitable concern.
The CdS film is lower than the light wave of 510nm as common absorbing wavelength of window material.The researcher proposes on the basis of analog computation, and the preparation of low thickness, fine and close CdS film is further to improve CuInSe
2One of key of class solar cell.Yet, adopt the CdS film of chemical bath deposition preparation to have short texture, acid resistance difference and and SnO
2With problem such as the glass adhesive force is relatively poor.This method is responsive to various process conditions such as depositing temperature, pH value, reaction solution concentration and mixing speed, reaction vessel size shape etc. in preparation process simultaneously, and these factors all have a significant effect to CdS optimal deposition time and deposition quality.Process conditions select incorrect meeting to cause the CdS crystal grain that is mingled with the yardstick inequality in the generation of second phase in the made CdS film or the film, and all these will finally have influence on adhering to and photoelectric characteristic of CdS film.
Utilizing traditional C dS thin film preparation process is magnetic agitation, and sedimentation time differs several seconds kinds, just can stick or grow into the inhomogeneous micelle of large scale in film surface and film.By prior art documents, find: Chinese patent application 96123704.X, the name of patent application is called: the method for solution growing semiconductor film, patent application is artificial: Cui Haining, Wang Rong etc., this patent is improved original process conditions by the mode of ultrasonic stirring, prepares fine and close CdS film.Ultrasonic stirring can be smashed the large scale micelle that occurs in the solution growth process, reaches the effect of homogeneous film, but the CdS film crystallite dimension that the ultrasonic stirring mode is grown is little.In photoelectric conversion process, crystal boundary is as a kind of common charge carrier complex centre, and crystallite dimension has a significant effect to the performance of device.
Summary of the invention
The objective of the invention is to overcome deficiency of the prior art, a kind of photovoltaic semiconductors film plating bath and preparation method thereof is provided.Adopt to add the method for polyethylene glycol in this preparation process, need not to force to stir, prepared CdS film homogeneous grain size, tack is good, optical transmittance is high.
The present invention is achieved by the following technical solutions, and the bath composition percentage by weight is: CdCl
20.06-0.3%, NH
4NO
31-3.32%, KOH 1.2-6%, CS (NH
2)
20.3-15%, polyethylene glycol are 0.2-0.8%, and all the other are deionized water.
This photovoltaic semiconductors method for manufacturing thin film can prepare the CdS film of big crystallite dimension, and it is compound effectively to have reduced diffuse scattering of CdS Film Optics and the crystal boundary of charge carrier in device.By the mode of simple interpolation polyethylene glycol, on the basis of simplifying original technology, prepared the CdS film of even compact, institute's made membrane shows good optical characteristics simultaneously.In chemical bath deposition CdS thin-film process, deposition reaction is carried out simultaneously at solution inside, substrate surface, in the course of reaction NH is arranged simultaneously
3Accessory substance generates.The mode that original process conditions are by mechanical forced stirring (magnetic agitation or ultrasonic stirring) prevents NH
3In substrate surface absorption, gathering, reach and drive NH
3Effect.NH
3Absorption, gathering at substrate surface can stop the growth of CdS in this zone, are the main causes that causes made film surface hole, pin hole.The major defect that mechanical forced stirs is, deposition along with CdS, the CdS particle that liquid phase generates constantly collides with substrate surface under churned mechanically drive, finally cause liquid-phase reaction product being mingled with in film, this CdS granular size that is mingled with differs, and can cause the more optics diffuse scattering of film, when process conditions are selected when improper, also can be the key factor that the film tack weakens, need avoid.
Concrete preparation process further describes as follows:
1, substrate passes through acetone, deionized water ultrasonic waves for cleaning, dry for standby successively.
2, the plating bath layoutprocedure is for adding the CdCl of certain volume successively in beaker
2, KOH, NH
4NO
3Solution and polyglycol solution stir, and utilize KOH to regulate plating bath to suitable pH value, place 20min.
3, treat that plating bath is stable after, water-bath is heated to 60-90 ℃, adds the thiourea solution for preparing in advance, mixes, and vertically puts into substrate, coating process begins.
4, deposition finishes, and removes the CdS particle that film surface adheres to by the mode of ultrasonic waves for cleaning.
According to the thickness of required film, whole deposition process is 0.5-1hr.As the thicker CdS film of needs, can repeat plating, to reach the film of desired thickness.
Compared with the prior art, the present invention has substantive distinguishing features and marked improvement, and its useful effect is:
1, further simplifies prior art, utilized the adding of surfactant polyethylene to replace original pressure stirring.The removal of forcing to stir has effectively suppressed liquid deposition CdS particle being mingled with in the CdS film, and made film particles size is even, and tack is good.
2, the growth pattern that leaves standstill helps bulky grain CdS growth for Thin Film, and compared with prior art, the crystallite dimension of the made CdS film of the present invention is bigger.This will help improving the photoelectric conversion efficiency of film, and it is compound to reduce the charge carrier crystal boundary.
3, institute's made membrane homogeneous grain size has reduced the diffuse scattering that original technology institute made membrane grain size inequality causes.Under identical conditions, compared with prior art, institute of the present invention made membrane has obviously higher light transmission rate.
4, good, the free of pinholes of the made adhesive force of the present invention, densification, evenly.The made film quality of whole technology is stable, the rate of finished products height.
Embodiment
Enumerate four embodiment below as further instruction:
Embodiment 1
Photovoltaic semiconductors film bath composition percentage by weight is: caddy (CdCl
2) 0.06%, ammonium nitrate (NH
4NO
3) 3.32%, potassium hydroxide (KOH) 6%, thiocarbamide (CS (NH
2)
2) 0.3%, polyethylene glycol 0.2%, bath temperature are controlled to be 60 ℃, and sedimentation time is 40min, and sizes of substrate is 2cm * 4cm slide and the aluminium flake of removing oily trowel used for plastering. after deposition finishes, utilize ultrasonic cleaning to remove the CdS particle that film surface adheres to.
The CdS film of made glass substrate light transmission rate height in the 520-1100nm scope, absorption band is precipitous.CdS film to two kinds of substrates of different carries out the test of mightiness belt adhesive force, and film does not have any peeling phenomenon to be taken place, CdS film surface light, even.
Embodiment 2
Photovoltaic semiconductors film bath composition percentage by weight is: caddy (CdCl
2) 0.18%, ammonium nitrate (NH
4NO
3) 2.16%, potassium hydroxide (KOH) 3.6%, thiocarbamide (CS (NH
2)
2) 15%, polyethylene glycol 0.2%, bath temperature are controlled to be 75 ℃, and sedimentation time is 40min, and sizes of substrate is 2cm * 4cm slide.After deposition finishes, utilize ultrasonic cleaning to remove the CdS particle that film surface adheres to.
Made CdS film light transmission rate height in the 520-1100nm scope.The CdS film is carried out the test of mightiness belt adhesive force, and film does not have any peeling phenomenon to be taken place, CdS film surface light, even.
Embodiment 3
Photovoltaic semiconductors film bath composition percentage by weight is: caddy (CdCl
2) 0.3%, ammonium nitrate (NH
4NO
3) 2.16%, potassium hydroxide (KOH) 3.6%, thiocarbamide (CS (NH
2)
2) 7.65%, polyethylene glycol 0.8%, bath temperature are controlled to be 75 ℃, and sedimentation time is 40min, and sizes of substrate is 2cm * 4cm slide.After deposition finishes, utilize ultrasonic cleaning to remove the CdS particle that film surface adheres to.
Made CdS film light transmission rate height in the 520-1100nm scope.Film is carried out the test of mightiness belt adhesive force, and film does not have any peeling phenomenon to be taken place, CdS film surface light, even.
Embodiment 4
Photovoltaic semiconductors film bath composition percentage by weight is: caddy (CdCl
2) 0.07%, ammonium nitrate (NH
4NO
3) 1%, potassium hydroxide (KOH) 1.2%, thiocarbamide (CS (NH
2)
2) 0.3%, polyethylene glycol 0.5%, bath temperature are controlled to be 90 ℃, and sedimentation time is 40min, and sizes of substrate is 2cm * 4cm slide.After deposition finishes, utilize ultrasonic cleaning to remove the CdS particle that film surface adheres to.
Made CdS film light transmission rate height in the 520-1100nm scope.Film is carried out the test of mightiness belt adhesive force, and film does not have any peeling phenomenon to be taken place, CdS film surface light, even.
Claims (4)
1, a kind of photovoltaic semiconductors film plating bath is characterized in that its weight percentages of components is: CdCl
20.06-0.3%, NH
4NO
31-3.32%, KOH1.2-6%, CS (NH
2)
20.3-15%, polyethylene glycol are 0.2-0.8%, and all the other are deionized water.
2, a kind of photovoltaic semiconductors method for manufacturing thin film is characterized in that, by adding the mode of polyethylene glycol, has prepared the CdS film of even compact.
According to the described photovoltaic semiconductors method for manufacturing thin film of claim 1, it is characterized in that 3, concrete preparation process further describes as follows:
(1) substrate passes through acetone, deionized water ultrasonic waves for cleaning, dry for standby successively;
(2) the solution allocation process is for adding CdCl successively in beaker
2, KOH, NH
4NO
3Solution and polyglycol solution stir, and utilize KOH to regulate plating bath to suitable pH value, place 20min;
(3) treat solution-stabilized after, water-bath is heated to 60-90 ℃, adds the thiourea solution prepare in advance, after mixing, vertically puts into substrate, coating process promptly begins;
(4) after deposition finishes, remove the CdS particle that film surface adheres to by the mode of ultrasonic waves for cleaning.
According to the described photovoltaic semiconductors method for manufacturing thin film of claim 1, it is characterized in that 4, according to the thickness of required film, whole deposition process is 0.5-1hr.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100167716A CN1295765C (en) | 2004-03-04 | 2004-03-04 | Photovoltaic semiconductor thin film plating liquid and its preparation method |
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|---|---|---|---|
| CNB2004100167716A CN1295765C (en) | 2004-03-04 | 2004-03-04 | Photovoltaic semiconductor thin film plating liquid and its preparation method |
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| Publication Number | Publication Date |
|---|---|
| CN1560910A true CN1560910A (en) | 2005-01-05 |
| CN1295765C CN1295765C (en) | 2007-01-17 |
Family
ID=34440643
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|---|---|---|---|
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100346457C (en) * | 2006-01-17 | 2007-10-31 | 湖南师范大学 | Production and producer for cadmium sulfide |
| CN100418201C (en) * | 2005-08-05 | 2008-09-10 | 中国科学院长春光学精密机械与物理研究所 | Production of thin-magnetic semiconductor epitaxial-thin-film of iron-doped cadmium sulfide |
| CN101820028A (en) * | 2010-02-11 | 2010-09-01 | 昆山正富机械工业有限公司 | Deposition method of multi-section camium sulfide thin film |
| CN102683485A (en) * | 2012-04-23 | 2012-09-19 | 江苏申乾食品包装有限公司 | Manufacture method of solar back plate |
| CN103824896A (en) * | 2006-02-23 | 2014-05-28 | 耶罗恩·K·J·范杜伦 | High-throughput printing of semiconductor precursor layer from inter-metallic nanoflake particles |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101820018B (en) * | 2009-02-27 | 2014-12-17 | 比亚迪股份有限公司 | Preparation method of CdS thin-film |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1136209A (en) * | 1966-06-17 | 1968-12-11 | Fuji Photo Film Co Ltd | Process for electrolytic electrophotography |
| JPS55102279A (en) * | 1979-01-30 | 1980-08-05 | Agency Of Ind Science & Technol | Method of fabricating photovoltaic element |
| US4287383A (en) * | 1979-12-26 | 1981-09-01 | Chevron Research Company | Cadmium sulfide photovoltaic cell of improved efficiency |
| CN1186770A (en) * | 1996-12-30 | 1998-07-08 | 中国科学院长春应用化学研究所 | Method of solution growing semiconductor film |
-
2004
- 2004-03-04 CN CNB2004100167716A patent/CN1295765C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100418201C (en) * | 2005-08-05 | 2008-09-10 | 中国科学院长春光学精密机械与物理研究所 | Production of thin-magnetic semiconductor epitaxial-thin-film of iron-doped cadmium sulfide |
| CN100346457C (en) * | 2006-01-17 | 2007-10-31 | 湖南师范大学 | Production and producer for cadmium sulfide |
| CN103824896A (en) * | 2006-02-23 | 2014-05-28 | 耶罗恩·K·J·范杜伦 | High-throughput printing of semiconductor precursor layer from inter-metallic nanoflake particles |
| CN101820028A (en) * | 2010-02-11 | 2010-09-01 | 昆山正富机械工业有限公司 | Deposition method of multi-section camium sulfide thin film |
| CN102683485A (en) * | 2012-04-23 | 2012-09-19 | 江苏申乾食品包装有限公司 | Manufacture method of solar back plate |
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| CN1295765C (en) | 2007-01-17 |
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Granted publication date: 20070117 Termination date: 20100304 |