CN102820380A - Method for improving insulating property of laser marked transparent conducting oxide thin film - Google Patents
Method for improving insulating property of laser marked transparent conducting oxide thin film Download PDFInfo
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- CN102820380A CN102820380A CN2012103085021A CN201210308502A CN102820380A CN 102820380 A CN102820380 A CN 102820380A CN 2012103085021 A CN2012103085021 A CN 2012103085021A CN 201210308502 A CN201210308502 A CN 201210308502A CN 102820380 A CN102820380 A CN 102820380A
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Abstract
The invention relates to a method for improving the insulating property of a laser marked transparent conducting oxide thin film, belonging to the technical field of a thin film solar battery. The method provided by the invention comprises the following technique steps of: (1) preparing a suede transparent conducting oxide thin film by using a process integrating magnetron sputtering and wet etching; (2) marking out the suede transparent conducting oxide thin film by using a laser device with a wavelength of 355 nm in an insulated manner; and (3) annealing the laser marked transparent conducting oxide thin film, so as to obtain a laser marked line with a good insulation property. The method provided by the invention can be compatible with the conventional production process of the thin film solar battery; an oxide thin film can be successfully marked by using the frequently-used 355-nm laser of a thin film solar battery assembly line, so that the marking quality is improved, and the production cost is reduced; the laser marking appearance is good, and the insulation property meets requirements of the production process; the process operation is simple; and the method provided by the invention is applicable to a silicon-based series thin film battery, a cadmium telluride series thin film battery, and the like.
Description
Technical field
The invention belongs to technical field of thin-film solar, specifically a kind of laser that improves is drawn the method for carving the transparent conductive oxide film insulation property.
Background technology
Grow with each passing day to the demand of the solar battery product that green energy resource especially extensively is suitable in countries in the world.Along with the development of technology, the solar cell user proposes higher requirement to the cost performance of battery component.Lower and conversion efficiency promotes the favor that receives the users that get more and more to the thin-film solar cells silicon-based film solar cells that particularly manufacturing process is ripe relatively steadily owing to its price.
Silicon-base thin-film battery main production process is: front glass cleans, and preceding electro-deposition, laser are drawn quarters (P1), the photoelectric conversion layer deposition, and laser is drawn quarter (P2), and back electrode deposits, and laser is drawn quarter (P3), and electrode is drawn, is encapsulated, test etc.Adopt laser equipment that depositional coating is carried out at a high speed, accurately draws quarter, continuous functional film layer is subdivided into single sub-battery, and between single sub-battery, sets up the series and parallel syndeton.This series and parallel structure is converted into low current, high voltage output characteristic with high electric current, low-voltage output characteristic, is to reduce ohm power loss essential condition.Therefore in the silicon-base thin-film battery production process, laser scribing is very crucial operation.
The P1 of electrode film drew carving technology before laser among the present invention was drawn the pointer body and is meant, purpose is to be divided into junior unit to electrode film before the large tracts of land, and requires to insulate between each junior unit, with the preceding electrode as follow-up each sub-battery.If insulation property are bad; Just possible conducting between the follow-up sub-battery; Cause one of them sub-battery conductively-closed to be fallen thereby the preceding electrode of adjacent sub-battery is coupled together,, can influence the sub-battery number of battery if these situation exist in a large number; Cause open circuit voltage to reduce, finally influence the photoelectric conversion efficiency of hull cell.Drawing of P1 carved except requiring insulation; Also require pattern good; So that carry out place mat for following one coating process; Increase like the bad silicon thin film defective of subsequent deposition that might cause of pattern; Cause that electric leakage appears in battery; Increase parallel resistance, reduce open-circuit voltage, finally influence the photoelectric transformation efficiency of battery; The glass that also should try one's best not to the bottom of draw carving of P1 causes damage in addition, to guarantee the long-term reliability of assembly.
Judge that P1 draws the resistance value that the index of carving the back insulation property is test line both sides, it is generally acknowledged that insulation resistance numerical value reaches 1 megaohm, can think to draw to be carved into merit.Insulating resistance value is higher than 1 megaohm, shows that rete scratches fully, and laser scribing reaches insulation function.Insulation resistance is lower than 1 megaohm, shows that rete is not scratched or do not drawn to carve thoroughly or electrically-conductive debris influence etc. arranged.For the effect of testing laser line, promptly whether the resistance value of laser scribing both sides reaches technical standard, adopts multi-electrode engaged test platform (MCT) that laser is drawn the insulation property of carving back AZO film and tests.For example, be slit into 128 bar shaped subelements to large tracts of land AZO divided thin film, be arranged in order from left to right; 128 probes are set among the MCT; Can measure the insulating resistance value between the subelement simultaneously simultaneously by being pressed on 128 sub-cells, statistics is less than the insulating resistance value of 1 megaohm; The traveling probe position takes multiple measurements respectively, and for example 25 times, can record diverse location place insulation resistance, add up in 25 times insulating resistance value less than 1 megaohm, judge the line effect.MCT can be used for MEASUREMENTS OF THIN insulation resistance after laser scribing, adjacent each sub-cells is carried out the test of insulation resistance, and take multiple measurements at diverse location.Technical standard in process of production, for example, among all megger test results, insulation resistance is no more than 10 less than the point of 1 megaohm.Have only the line quality to satisfy technical standard, could guarantee the photoelectric conversion efficiency of assembly.
The laser that is used at present the P1 line in the industrialization process divides by wavelength to mainly contain two kinds of 355nm and 1064nm.The 1064nm infrared laser, because low, the single photon energy of its frequency is little, the course of processing mainly is to lean on the heat effect principle, working position heat fused, vaporization that desire is processed object become the gas loss then to be fallen, and therefore is referred to as hot working.From draw carving effect, thus the 1064nm laser for this heat treatment of rete itself can cause very big heat affected area destroy around film quality, draw in addition and carve the edge and produce projection, can influence the growth course of subsequent film etc., have a series of problem.And the 355nm ultraviolet laser, because its frequency is high, single photon energy is big, so can directly invade the interior keys knot of desiring film processed, high-energy photons is directly destroyed associative key and is formed the plasma loss and fall, so is referred to as cold working.Different with the infra-red heat processing, the rete that this cold treatment processes has very smooth edges, and processing edge fire damage and heat affected area are little.In addition, ZnO film itself also is a reason of selecting 355 laser to the difference absorption of different wavelengths of light.Therefore, the 355nm laser has been widely used in the middle of the commercial process of hull cell.
ZnO thin film doped optical absorption changes because of the difference of doped chemical kind and doping, and this characteristic also can be drawn the process and the result at quarter and exerts an influence using the 355nm laser to carry out P1 laser.ZnO thin film doped for B, the light absorption cut-off wavelength is greater than laser output wavelength 355nm, draws at laser therefore that film can fully absorb laser energy in the process at quarter, destroys associative key and forms the plasma loss and fall, the purpose that film is reached scratch fully.ZnO thin film doped for Al, the light absorption cut-off wavelength is near laser output wavelength 355nm, in the technical process; The variation of doping causes the light absorption cut-off wavelength to change; Can not fully absorb the laser energy of 355nm wavelength, it is relatively poor to cause draw carving effect, and the resistance of line both sides is lower; Technical standard in the inaccessible suitability for industrialized production, thus the electric property of hull cell influenced.
Summary of the invention
The objective of the invention is to above-mentioned technical problem, provide a kind of laser that improves to draw the method for carving the transparent conductive oxide film insulation property.
The technical scheme that the present invention takes:
A kind of laser that improves is drawn the method for carving the transparent conductive oxide film insulation property, may further comprise the steps: utilize magnetron sputtering to cooperate the technology of wet etching to prepare the matte transparent conductive oxide film; Adopting wavelength is that the laser of 355nm or 1064nm is to the line of insulating of said matte transparent conductive oxide film; The matte transparent conductive oxide film that will pass through laser scribing carries out annealing in process and gets final product.
Said transparent conductive oxide film comprises AZO film, F doping SnO
2Film, Sn doping In
2O
3Film or B are ZnO thin film doped.
Said magnetron sputtering mode comprises straight frequency, intermediate frequency or radio frequency.
The substrate deposition temperature is 0 ~ 300 ℃ during said magnetron sputtering, and film thickness is 0.3 ~ 2 micron.
The employed etching solution of said wet etching is inorganic acid, alkali or the salt of dilution.Said annealing in process is cycle annealing, high temperature rapid thermal annealing or temperature gradual change annealing.
Advantage of the present invention and good effect:
1) production technology of this method and existing thin-film solar cells is compatible; Adopt production line common 355nm or 1064nm laser and cooperate subsequent anneal to handle and to obtain the good AZO film of insulation property; Need not purchase the laser of lower wavelength, greatly reduce production cost.
2) line good insulation preformance, scribing edge is smooth and deposit bead hardly, helps the growth of subsequent film.
3) the laser technical parameters scope is wide, regulates flexibly, and is simple to operate.
4) the present invention is unrestricted to the transparent conductive oxide film preparation condition, the film that comes out applicable to any condition deposit.
5) the present invention and existing industrialized producing technology are compatible, are applicable to hull cells such as silica-based series thin film battery, cadmium telluride series thin film battery.
6) annealing process of the present invention is flexible, and technological parameters such as annealing temperature, annealing time can in very large range be regulated, the process window broad.
Description of drawings
Fig. 1 is a process flow diagram of the present invention.
Fig. 2 a and Fig. 2 b be respectively embodiment after 1 stroke of quarter before the annealing of matte AZO film with annealing after the MCT test result.
Fig. 3 a and Fig. 3 b be respectively embodiment after 2 strokes of quarters before the annealing of matte AZO film with annealing after the MCT test result.
Fig. 4 a and Fig. 4 b be respectively embodiment after 3 strokes of quarters before the annealing of matte AZO film with annealing after the MCT test result.
Embodiment
Below in conjunction with accompanying drawing, the present invention is further specified through embodiment.
As shown in Figure 1, the preparation of present embodiment matte AZO film and stroke carving technology method are following:
1, utilize semicon industry to use cleaning agent always, clean the ultra-white float glass substrate of 1.3m * 1.1m, remove organic spot, the dust of substrate surface, clean with pure water rinsing, oven dry.
2, adopt magnetically controlled sputter method, the substrate deposition temperature is 25
oC, obtaining thickness is the large tracts of land ZnO:Al transparent conductive film about 900nm.
3, the ZnO:Al film to the 1.1mX1.3m area carries out the wet chemical etching processing in wet etching equipment, and etching solution is 0.5% watery hydrochloric acid, etching temperature 25
oC, substrate transport speed is 2000mm/min.
4, matte AZO film is placed stroke quarter of insulating under the laser board 355nm, laser head power is 0.41-0.43W.
5, will draw film after quarter under vacuum, underlayer temperature 450
oC, annealing in process 20min.
Fig. 2 a and Fig. 2 b have provided the MCT test result of AZO film before and after annealing in process in the case study on implementation 1 respectively, and insulation resistance is lower than the point of 1 megaohm and reduces to 1 by 8 before annealing.
The preparation of present embodiment matte AZO film and stroke carving technology method are following:
Like embodiment 1 preparation and processing method, during etching, substrate transport speed is 1600mm/min.
Fig. 3 a and Fig. 3 b have provided the MCT test result of AZO film before and after annealing in process in the case study on implementation 2 respectively, and insulation resistance is lower than the point of 1 megaohm and reduces to 1 by 30 before annealing.
1, utilize semicon industry to use cleaning agent always, clean the ultra-white float glass substrate of 1.3m * 1.1m, remove organic spot, the dust of substrate surface, clean with pure water rinsing, oven dry.
2, adopt magnetically controlled sputter method, the substrate deposition temperature is 230
oC, obtaining thickness is the large tracts of land ZnO:Al transparent conductive film about 850nm.
3, in large tracts of land wet etching equipment, large tracts of land ZnO:Al film is carried out the wet chemical etching processing.Etching solution is 0.5% watery hydrochloric acid, at etching temperature 26
oCarry out dynamic etching under C, the substrate translational speed 2000mm/min condition.
4, matte AZO film is placed stroke quarter of insulating under the laser board 355nm, laser head power is 0.41-0.43W.
5, will draw film after quarter under vacuum, underlayer temperature 450
oC, annealing in process 20min.
Fig. 4 a and Fig. 4 b have provided the MCT test result of AZO film before and after annealing in process in the case study on implementation 3 respectively, and insulation resistance is lower than the point of 1 megaohm and reduces to 4 by 54 before annealing.
The film that the inventive method laser is drawn quarter is a transparent conductive oxide film, is not limited only to the AZO film, also comprises F doping SnO
2Film, Sn doping In
2O
3ZnO thin film doped other kind transparent conductive oxide films that waits of film and B; Laser wavelength is not only limited to 355nm, can be 1064nm yet; Annealing in process can comprise cycle annealing, polytypes such as high temperature rapid thermal annealing and temperature gradual change annealing.
Claims (6)
1. one kind is improved the method that laser is drawn transparent conductive oxide film insulation property at quarter, it is characterized in that may further comprise the steps: utilize magnetron sputtering to cooperate the technology of wet etching to prepare the matte transparent conductive oxide film; Adopting wavelength is that the laser of 355nm or 1064nm is to the line of insulating of said matte transparent conductive oxide film; The matte transparent conductive oxide film that will pass through laser scribing carries out annealing in process and gets final product.
2. method according to claim 1 is characterized in that said transparent conductive oxide film is AZO film, F doping SnO
2Film, Sn doping In
2O
3Film or B are ZnO thin film doped.
3. method according to claim 1 is characterized in that said magnetron sputtering mode is straight frequency, intermediate frequency or radio frequency.
4. method according to claim 1, the substrate deposition temperature is 0 ~ 300 ℃ when it is characterized in that said magnetron sputtering, film thickness is 0.3 ~ 2 micron.
5. method according to claim 1 is characterized in that inorganic acid, alkali or the salt of the employed etching solution of said wet etching for dilution.
6. method according to claim 1 is characterized in that said annealing in process is cycle annealing, high temperature rapid thermal annealing or temperature gradual change annealing.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104253177A (en) * | 2013-06-28 | 2014-12-31 | 台积太阳能股份有限公司 | Nozzle assembly and method for fabricating solar cell |
| CN114141958A (en) * | 2021-12-02 | 2022-03-04 | 中国华能集团清洁能源技术研究院有限公司 | Processing method and battery of photovoltaic conductive FTO glass |
| CN114325099A (en) * | 2021-11-29 | 2022-04-12 | 无锡极电光能科技有限公司 | Thin-film solar cell insulated wire resistance online testing device and method |
| CN114388701A (en) * | 2022-01-17 | 2022-04-22 | 华能新能源股份有限公司 | Manufacturing method of perovskite battery |
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| CN1089756A (en) * | 1992-07-21 | 1994-07-20 | 株式会社半导体能源研究所 | The manufacture method of semiconductor device and manufacture method thereof and transparent conductive film |
| US20080029152A1 (en) * | 2006-08-04 | 2008-02-07 | Erel Milshtein | Laser scribing apparatus, systems, and methods |
| CN101807622A (en) * | 2009-02-12 | 2010-08-18 | 四川尚德太阳能电力有限公司 | Method for manufacturing cadmium telluride thin film solar cell modules |
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2012
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Patent Citations (5)
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| CN1089756A (en) * | 1992-07-21 | 1994-07-20 | 株式会社半导体能源研究所 | The manufacture method of semiconductor device and manufacture method thereof and transparent conductive film |
| US20080029152A1 (en) * | 2006-08-04 | 2008-02-07 | Erel Milshtein | Laser scribing apparatus, systems, and methods |
| CN101842900A (en) * | 2007-08-30 | 2010-09-22 | 欧瑞康太阳Ip股份公司（特吕巴赫） | A thin-film solar cell system and method and apparatus for manufacturing a thin-film solar cell |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104253177A (en) * | 2013-06-28 | 2014-12-31 | 台积太阳能股份有限公司 | Nozzle assembly and method for fabricating solar cell |
| CN104253177B (en) * | 2013-06-28 | 2017-01-11 | 台湾积体电路制造股份有限公司 | Nozzle assembly and method for fabricating solar cell |
| CN114325099A (en) * | 2021-11-29 | 2022-04-12 | 无锡极电光能科技有限公司 | Thin-film solar cell insulated wire resistance online testing device and method |
| CN114141958A (en) * | 2021-12-02 | 2022-03-04 | 中国华能集团清洁能源技术研究院有限公司 | Processing method and battery of photovoltaic conductive FTO glass |
| CN114388701A (en) * | 2022-01-17 | 2022-04-22 | 华能新能源股份有限公司 | Manufacturing method of perovskite battery |
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Application publication date: 20121212 |