MD4377C1 - Semiconductor photoelectric converter and method for manufacturing thereof - Google Patents
Semiconductor photoelectric converter and method for manufacturing thereof Download PDFInfo
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- MD4377C1 MD4377C1 MDA20100068A MD20100068A MD4377C1 MD 4377 C1 MD4377 C1 MD 4377C1 MD A20100068 A MDA20100068 A MD A20100068A MD 20100068 A MD20100068 A MD 20100068A MD 4377 C1 MD4377 C1 MD 4377C1
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- 239000004065 semiconductor Substances 0.000 claims abstract description 49
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 48
- 239000000956 alloy Substances 0.000 claims abstract description 48
- 239000002159 nanocrystal Substances 0.000 claims abstract description 31
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 24
- 239000010703 silicon Substances 0.000 claims abstract description 24
- 229910000679 solder Inorganic materials 0.000 claims abstract description 16
- 239000000853 adhesive Substances 0.000 claims abstract description 14
- 230000001070 adhesive effect Effects 0.000 claims abstract description 14
- 230000005686 electrostatic field Effects 0.000 claims abstract description 14
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 12
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000004519 manufacturing process Methods 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 6
- 239000003792 electrolyte Substances 0.000 claims abstract description 6
- 239000012153 distilled water Substances 0.000 claims abstract description 5
- 239000012535 impurity Substances 0.000 claims abstract description 5
- 229910052751 metal Inorganic materials 0.000 claims abstract description 5
- 239000002184 metal Substances 0.000 claims abstract description 5
- 230000000737 periodic effect Effects 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 5
- QVYYOKWPCQYKEY-UHFFFAOYSA-N [Fe].[Co] Chemical compound [Fe].[Co] QVYYOKWPCQYKEY-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000005275 alloying Methods 0.000 claims abstract description 4
- WBYRVEAPTWYNOX-UHFFFAOYSA-N [Fe].[Cd] Chemical compound [Fe].[Cd] WBYRVEAPTWYNOX-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000010410 layer Substances 0.000 claims description 31
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 9
- 238000005476 soldering Methods 0.000 claims description 7
- 239000003292 glue Substances 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 4
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical class Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 229940044175 cobalt sulfate Drugs 0.000 claims description 3
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 3
- 239000011241 protective layer Substances 0.000 claims description 3
- 229910000925 Cd alloy Inorganic materials 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 7
- LQBJWKCYZGMFEV-UHFFFAOYSA-N lead tin Chemical compound [Sn].[Pb] LQBJWKCYZGMFEV-UHFFFAOYSA-N 0.000 abstract description 4
- 239000000203 mixture Substances 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 2
- 238000007747 plating Methods 0.000 abstract 1
- 239000011253 protective coating Substances 0.000 abstract 1
- 239000010408 film Substances 0.000 description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 230000005684 electric field Effects 0.000 description 4
- 230000001681 protective effect Effects 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 230000005865 ionizing radiation Effects 0.000 description 2
- 231100000289 photo-effect Toxicity 0.000 description 2
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 229910000531 Co alloy Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910021577 Iron(II) chloride Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000004054 semiconductor nanocrystal Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000010626 work up procedure Methods 0.000 description 1
Classifications
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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
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- Photovoltaic Devices (AREA)
Abstract
Description
Invenţia se referă la tehnica de conversie a energiei radiaţiei solare în energie electrică, în particular, la construcţia contactelor şi la compoziţia chimică a materialelor, utilizate la fabricarea elementelor conducătoare de curent şi semiconductoare ale convertorului fotovoltaic. The invention refers to the technique of converting the energy of solar radiation into electrical energy, in particular, to the construction of the contacts and the chemical composition of the materials, used in the manufacture of the current-conducting and semi-conducting elements of the photovoltaic converter.
Se cunoaşte compoziţia şi tehnologia de fabricare a peliculei subţiri din semiconductor din siliciu policristalin hidrogenat cu dimensiunile medii ale cristalelor mai mici de 10 nm conţinând peste 50% de fază cristalină [1]. The composition and manufacturing technology of the thin film of hydrogenated polycrystalline silicon semiconductor with average crystal sizes of less than 10 nm containing over 50% of crystalline phase is known [1].
Dezavantajul acestei pelicule constă în faptul că în conţinutul acesteia sunt până la 40% de siliciu amorf, ceea ce duce la scăderea eficacităţii energetice a convertorului şi creează necesitatea măririi corespunzătoare a suprafeţei iradiate a semiconductorului în scopul de a mări intensitatea curentului până la valori maxime posibile. The disadvantage of this film is that it contains up to 40% of amorphous silicon, which leads to a decrease in the energy efficiency of the converter and creates the need to increase the irradiated surface of the semiconductor in order to increase the current intensity to the maximum possible values .
Se cunoaşte, de asemenea, contactul de pelicule groase între semiconductorul de siliciu cristalin şi electrozii conductori de curent, care constau din pastă cu conţinut de argint, aplicată pe ambele părţi ale semiconductorului şi prelucrată termic, acoperită în partea din spate cu aliaj de lipit pe bază de cositor, iar în partea iluminată - cu aliaj de lipit şi cu acoperire de nichel [2]. Thick film contact between crystalline silicon semiconductor and current-conducting electrodes is also known, consisting of silver-containing paste, applied to both sides of the semiconductor and heat-treated, coated on the back side with solder alloy on tin base, and in the illuminated part - with soldering alloy and nickel coating [2].
Dezavantajul acestui contact constă în faptul că utilizarea fondantului în timpul cositoririi şi lipirii duce la scurgerea acestuia pe suprafaţa de lucru a semiconductorului, ecranarea parţială a acesteia, micşorarea suprafeţei active, micşorarea eficacităţii energetice a celulei. Utilizarea nichelului pentru acoperirea fâşiilor subţiri colectoare de curent măreşte rezistenţa electrică a acestora şi duce la un consum suplimentar de energie electrică produsă la încălzirea semiconductorului, iar utilizarea fâşiilor colectoare de curent prefabricate complică procesul de fabricare şi reduce fiabilitatea convertorului. The disadvantage of this contact is that the use of fondant during tinning and gluing leads to its leakage on the working surface of the semiconductor, its partial shielding, the reduction of the active surface, the reduction of the energy efficiency of the cell. The use of nickel to cover thin current collector strips increases their electrical resistance and leads to additional consumption of electricity produced when heating the semiconductor, and the use of prefabricated current collector strips complicates the manufacturing process and reduces the reliability of the converter.
Cea mai apropiată soluţie este convertorul fotovoltaic semiconductor, care conţine o placă din semiconductor, pe suprafaţa din spate a căreia este aplicat un strat de aliaj de lipit din cositor-plumb, iar pe suprafaţa frontală sunt aplicate contacte metalice colectoare de curent din argint şi nichel (sau din titan) şi un strat de adeziv organosilicic, cu ajutorul căruia de placă se fixează o acoperire de sticlă de protecţie, pe care este aplicată o peliculă hidrofobă. Sticla utilizată este executată cu posibilitatea formării unui câmp electric interior la acţiunea radiaţiei ionizante [3]. The closest solution is the semiconductor photovoltaic converter, which contains a semiconductor plate, on the back surface of which a tin-lead solder alloy layer is applied, and on the front surface silver and nickel current collector metal contacts are applied (or titanium) and a layer of organosilicon adhesive, with the help of which a protective glass cover is fixed to the plate, on which a hydrophobic film is applied. The glass used is executed with the possibility of forming an internal electric field under the action of ionizing radiation [3].
Dezavantajele acestui convertor constau în: utilizarea fondantului în timpul cositoririi suprafeţei din spate a plăcii din semiconductor, ceea ce duce ulterior la utilizarea incompletă a suprafeţei active a acesteia, la micşorarea suprafeţei de contact a cristalelor semiconductorului cu aliajul de lipit din cauza pătrunderii fondantului în adâncituri şi a ecranării de către acesta a unei porţiuni a suprafeţei reale a nanocristalelor semiconductorului, care la utilizarea în fotoefect ar putea mări conductibilitatea electrică a stratului de tranziţie şi eficacitatea energetică a convertorului fotovoltaic. Utilizarea plăcii policristaline din siliciu cu plane cristalografice parţial orientate duce la scăderea randamentului de curent al fiecărei unităţi de volum a materialului semiconductor. Aplicarea pe partea frontală a convertorului fotovoltaic a pastei cu conţinut de argint la executarea fâşiilor colectoare de curent înguste este legată de asemenea cu murdărirea şi ecranarea unei porţiuni a suprafeţei de lucru a plăcii cu substanţele liante, reducerea clarităţii ei optice şi înrăutăţirea rezultatelor fotoefectului. Utilizarea sticlei de protecţie cu acoperire hidrofobă micşorează puterea de ieşire a convertorului fotovoltaic, conform rezultatelor experimentale, cel puţin cu 17...20%. Crearea cu ajutorul sticlei metalizate de protecţie a câmpului electric, care frânează electronii, duce la micşorarea energiei razelor solare şi puterii specifice de ieşire. The disadvantages of this converter are: the use of fondant during tinning of the back surface of the semiconductor board, which subsequently leads to the incomplete use of its active surface, the reduction of the contact surface of the semiconductor crystals with the solder alloy due to the penetration of the fondant into the recesses and the shielding by it of a portion of the real surface of the semiconductor nanocrystals, which when used in the photoeffect could increase the electrical conductivity of the transition layer and the energy efficiency of the photovoltaic converter. The use of the polycrystalline silicon plate with partially oriented crystallographic planes leads to a decrease in the current yield of each volume unit of the semiconductor material. The application on the front side of the photovoltaic converter of the paste containing silver when making the narrow current collector strips is also related to soiling and shielding a portion of the working surface of the board with binder substances, reducing its optical clarity and worsening the photoeffect results. The use of protective glass with a hydrophobic coating reduces the output power of the photovoltaic converter, according to experimental results, at least by 17...20%. The creation with the help of metallized glass of protection of the electric field, which brakes the electrons, leads to the reduction of the energy of the solar rays and the specific output power.
Problema pe care o rezolvă invenţia constă în majorarea eficienţei energetice a convertorului fotovoltaic de 1,5 ori. The problem that the invention solves consists in increasing the energy efficiency of the photovoltaic converter by 1.5 times.
Convertorul fotovoltaic semiconductor, conform invenţiei, înlătură dezavantajele menţionate mai sus prin aceea că conţine un strat semiconductor, pe suprafaţa frontală a căruia sunt aplicate contacte metalice colectoare de curent şi un strat de adeziv organosilicic, iar pe suprafaţa opusă a stratului semiconductor este aplicat un strat de aliaj de lipit. Totodată stratul semiconductor este executat din nanocristale de siliciu, planele cristalografice ale cărora sunt orientate într-o direcţie. Aliajul de lipit pe bază de cositor conţine stibiu în cantitate de 3...4% din masa aliajului. Contactele colectoare de curent sunt confecţionate din aliaj galvanic de fier-cobalt sau de fier-cadmiu, iar stratul de protecţie din adeziv organosilicic cu grosimea de 0,17…0,2 mm este aplicat pe toate suprafeţele convertorului. The semiconductor photovoltaic converter, according to the invention, removes the disadvantages mentioned above in that it contains a semiconductor layer, on the front surface of which current collector metal contacts and a layer of organosilicon adhesive are applied, and on the opposite surface of the semiconductor layer a layer is applied of solder alloy. At the same time, the semiconductor layer is made of silicon nanocrystals, the crystallographic planes of which are oriented in one direction. The tin-based soldering alloy contains antimony in the amount of 3...4% of the mass of the alloy. The current collector contacts are made of galvanic iron-cobalt or iron-cadmium alloy, and the protective layer of organosilicon adhesive with a thickness of 0.17...0.2 mm is applied to all surfaces of the converter.
Procedeul de fabricare a convertorului fotovoltaic semiconductor, conform invenţiei, înlătură dezavantajele menţionate mai sus prin aceea că se orientează nanocristalele de siliciu prin rotirea unei surse de câmp electrostatic exterior în jurul stratului semiconductor cu pasul de rotire de 10° şi se determină experimental unghiul sub care se fixează sursa de câmp electrostatic exterior, se topeşte pelicula din aliaj de lipit pe bază de cositor aliat cu stibiu, se depun în aliaj nanocristalele de siliciu orientate cu alierea concomitentă a unei părţi de nanocristale cu stibiu şi se răceşte aliajul. Placa obţinută se cufundă într-o baie galvanică cu electrolit, care conţine soluţie apoasă, de exemplu, de sare a clorurii de fier - 360 g/L, sulfat de cobalt - 40 g/L la pH = 1,2...1,7 şi temperatura soluţiei de 313K, pentru asigurarea durabilităţii adeziunii aliajului galvanic cu semiconductorul până la 220 g/mm2 al suprafeţei de contact, se efectuează tratarea anodică a suprafeţei frontale a stratului semiconductor în decurs de 25 s la densitatea de amplitudine a curentului de 55...60 A/dm2, se fixează un şablon de suprafaţa frontală curăţită de oxizi şi de impurităţi a plăcii obţinute, se conectează placa cu catodul la o sursă de curent periodic cu impuls de retur reglabil după amplitudine şi după durată, şi la raportul amplitudinilor impulsului catodic şi celui anodic de curent egal cu 6:1, în decurs de 3 min se măreşte densitatea impulsului direct de la 0 până la 40 A/dm2, se depune aliajul galvanic în decurs de 12...20 min la raportul stabilit al curenţilor. Convertorul fotovoltaic obţinut se spală cu apă distilată la temperatura de ~330K, se usucă, se cufundă în adeziv organosilicic, se înlătură din vasul cu adeziv şi se usucă în dulapul de uscat la temperatura de 360K timp de 10 min. The manufacturing process of the semiconductor photovoltaic converter, according to the invention, removes the disadvantages mentioned above by orienting the silicon nanocrystals by rotating an external electrostatic field source around the semiconductor layer with a rotation step of 10° and experimentally determining the angle at which the source of the external electrostatic field is fixed, the solder alloy film based on tin alloyed with antimony is melted, the oriented silicon nanocrystals are deposited in the alloy with the simultaneous alloying of a part of the nanocrystals with antimony and the alloy is cooled. The plate obtained is immersed in a galvanic bath with electrolyte, which contains an aqueous solution, for example, of iron chloride salt - 360 g/L, cobalt sulfate - 40 g/L at pH = 1.2...1 ,7 and the temperature of the solution of 313K, to ensure the durability of the adhesion of the galvanic alloy with the semiconductor up to 220 g/mm2 of the contact surface, the anodic treatment of the front surface of the semiconductor layer is performed within 25 s at the current amplitude density of 55 ...60 A/dm2, fix a template to the front surface cleaned of oxides and impurities of the obtained plate, connect the plate with the cathode to a periodic current source with adjustable return pulse by amplitude and by duration, and at the ratio cathodic and anodic current pulse amplitudes equal to 6:1, within 3 min the density of the direct pulse is increased from 0 to 40 A/dm2, the galvanic alloy is deposited within 12...20 min at the established ratio of currents. The obtained photovoltaic converter is washed with distilled water at a temperature of ~330K, dried, immersed in organosilicon glue, removed from the pot with glue and dried in the drying cabinet at a temperature of 360K for 10 min.
Utilizarea construcţiei propuse a convertorului fotovoltaic semiconductor permite de a majora eficienţa energetică a procesului de conversie din contul rezultatului tehnic: îmbunătăţirea contactului electric între stratul aliajului de lipit şi nanocristalele de siliciu şi răcirea lor concomitentă; tratarea anodică electrochimică a suprafeţei frontale a stratului semiconductor cu un curent periodic cu impuls de retur reglabil după amplitudine şi după durată; obţinerea aliajului galvanic în regimurile, care asigură durabilitatea înaltă a adeziunii aliajului galvanic cu stratul semiconductor; formarea stratului de protecţie din adeziv organosilicic; utilizarea unor materiale conductoare de curent noi pentru anod şi catod. The use of the proposed construction of the semiconductor photovoltaic converter allows to increase the energy efficiency of the conversion process due to the technical result: the improvement of the electrical contact between the solder alloy layer and the silicon nanocrystals and their simultaneous cooling; electrochemical anodic treatment of the front surface of the semiconductor layer with a periodic current with return pulse adjustable by amplitude and duration; obtaining the galvanic alloy in the regimes, which ensure the high durability of the adhesion of the galvanic alloy with the semiconductor layer; formation of the protective layer of organosilicon adhesive; the use of new conductive materials for anode and cathode.
Experimental a fost constatată posibilitatea majorării curentului în circuitul exterior de 1,5 ori prin schimbarea direcţiei de orientare a planelor cristalografice ale nanocristalelor de siliciu în raport cu direcţia fluxului de lumină prin rotirea sursei de câmp electrostatic exterior, iar prin modificarea compoziţiei chimice a materialului anodului şi catodului - posibilitatea creşterii tensiunii electromotoare cu ~250 mV. Datele obţinute au fost utilizate pentru majorarea eficienţei energetice a convertorului fotovoltaic semiconductor. Aceste rezultate sunt confirmate experimental în procesul de testare a variantelor de construcţie şi de executare a convertoarelor fotovoltaice. Constructiv a fost obţinut curentul maxim posibil în circuitul exterior al convertorului fotovoltaic, au fost depistate condiţiile pentru obţinerea unei legături rezistente între contactele electrice şi nanocristalele de siliciu prin fuziunea aliajului de lipit modificat şi depunerea aliajelor galvanice pentru asigurarea contactelor conductoare durabile. Experimentally, the possibility of increasing the current in the external circuit by 1.5 times was found by changing the orientation direction of the crystallographic planes of the silicon nanocrystals in relation to the direction of the light flow by rotating the external electrostatic field source, and by changing the chemical composition of the anode material and the cathode - the possibility of increasing the electromotive voltage by ~250 mV. The obtained data were used to increase the energy efficiency of the semiconductor photovoltaic converter. These results are confirmed experimentally in the process of testing the construction and execution variants of the photovoltaic converters. Constructively, the maximum possible current was obtained in the external circuit of the photovoltaic converter, the conditions for obtaining a resistant bond between the electrical contacts and the silicon nanocrystals through the fusion of the modified solder alloy and the deposition of galvanic alloys to ensure durable conductive contacts were found.
Convertorul fotovoltaic semiconductor conţine un anod, executat din aliajul de lipit pe bază de cositor, care conţine stibiu în cantitate de ~4% din masa aliajului, stratul semiconductor din nanocristale de siliciu cu dimensiunile de cca 40 nm, un catod îngroşat, executat în formă de fâşii colectoare de curent cu grosimea de 0,17…0,2 mm, ceea ce conduce la compensarea pierderilor ohmice, majorarea durabilităţii şi durităţii stratului semiconductor, iar pentru executarea catodului sunt utilizate aliaje cu legătura interioară dintre electronii şi nucleele atomilor acestora mai puternică. The semiconductor photovoltaic converter contains an anode, made of tin-based soldering alloy, which contains stium in the amount of ~4% of the alloy mass, the semiconductor layer of silicon nanocrystals with dimensions of about 40 nm, a thickened cathode, made in the form of current collector strips with a thickness of 0.17...0.2 mm, which leads to the compensation of ohmic losses, increasing the durability and hardness of the semiconductor layer, and for the execution of the cathode, alloys with a stronger internal connection between the electrons and the nuclei of their atoms are used .
Procedeul se efectuează după cum urmează. The procedure is carried out as follows.
Se orientează nanocristalele de siliciu prin rotirea unei surse de câmp electrostatic exterior în jurul stratului semiconductor cu pasul de rotire de 10° pentru determinarea curentului maxim posibil în circuitul exterior în condiţiile date. Se determină experimental unghiul dintre axa verticală şi vectorul intensităţii câmpului electrostatic exterior, sub care se fixează sursa de câmp electrostatic exterior, se topeşte pelicula din aliaj de lipit pe bază de cositor aliat cu stibiu, se depun în aliaj nanocristalele de siliciu orientate cu alierea concomitentă a unei părţi de nanocristale cu stibiu şi se răceşte aliajul. Pe suprafeţele din spate şi laterale ale plăcii obţinute se depune un strat din adeziv organosilicic, după care placa se introduce în dulapul de uscat şi se usucă. Placa obţinută se cufundă într-o baie galvanică cu electrolit, care conţine soluţie apoasă de sare a clorurii de fier - 360 g/L, sulfat de cobalt - 40 g/L la pH = 1,2...1,7 şi temperatura soluţiei de 313K, pentru asigurarea durabilităţii adeziunii aliajului galvanic cu semiconductorul până la 220 g/mm2 al suprafeţei de contact, se efectuează tratarea anodică a suprafeţei frontale a stratului semiconductor în decurs de 25 s la densitatea de amplitudine a curentului de 55...60 A/dm2. De suprafaţa frontală curăţită de oxizi şi de impurităţi a plăcii obţinute se fixează un şablon, placa se conectează cu catodul la o sursă de curent periodic cu impuls de retur reglabil după amplitudine şi după durată, şi la raportul amplitudinilor impulsului catodic şi celui anodic de curent egal cu 6:1, în decurs de 3 min se măreşte densitatea impulsului direct de la 0 până la 40 A/dm2, pentru asigurarea unei legături rezistente între contactele electrice şi nanocristalele de siliciu, după care se depune aliajul galvanic în decurs de 15 min la raportul stabilit al curenţilor. Convertorul fotovoltaic obţinut se spală cu apă distilată la temperatura de ~330K, se usucă, se cufundă în adeziv organosilicic, se înlătură din vasul cu adeziv şi se usucă în dulapul de uscat la temperatura de 360K timp de 10 min. Orient the silicon nanocrystals by rotating an external electrostatic field source around the semiconductor layer with a rotation step of 10° to determine the maximum possible current in the external circuit under the given conditions. The angle between the vertical axis and the external electrostatic field intensity vector is experimentally determined, under which the external electrostatic field source is fixed, the tin-based soldering alloy film alloyed with staium is melted, the oriented silicon nanocrystals are deposited in the alloy with the simultaneous alloying of a part of nanocrystals with antimony and cool the alloy. A layer of organosilicon adhesive is deposited on the back and side surfaces of the obtained plate, after which the plate is inserted into the drying cabinet and dried. The plate obtained is immersed in a galvanic bath with electrolyte, which contains an aqueous solution of iron chloride salt - 360 g/L, cobalt sulfate - 40 g/L at pH = 1.2...1.7 and the temperature of the 313K solution, to ensure the durability of the adhesion of the galvanic alloy with the semiconductor up to 220 g/mm2 of the contact surface, the anodic treatment of the front surface of the semiconductor layer is performed within 25 s at the current amplitude density of 55...60 A/dm2. A template is attached to the front surface of the obtained plate cleaned of oxides and impurities, the plate is connected with the cathode to a periodic current source with a return pulse adjustable by amplitude and duration, and by the ratio of the amplitudes of the cathodic and anodic current pulses equal to 6:1, within 3 min the density of the direct impulse is increased from 0 to 40 A/dm2, to ensure a resistant bond between the electrical contacts and the silicon nanocrystals, after which the galvanic alloy is deposited within 15 min at the established current ratio. The obtained photovoltaic converter is washed with distilled water at a temperature of ~330K, dried, immersed in organosilicon glue, removed from the pot with glue and dried in the drying cabinet at a temperature of 360K for 10 min.
Ulterior convertorul fotovoltaic se testează prin iradierea acestuia cu radiaţie solară. Afterwards, the photovoltaic converter is tested by irradiating it with solar radiation.
Invenţia propusă permite: majorarea forţei electromotoare interioare între electrozi prin deplasarea potenţialului anodic propriu spre partea electropozitivă şi a celui catodic - spre partea electronegativă, majorarea curentului maxim posibil al convertorului semiconductor prin orientarea nanocristalelor de siliciu într-un câmp electrostatic exterior, majorarea diferenţei de potenţial dintre anod şi catod prin utilizarea unor aliaje galvanice cu valori ridicate ale potenţialelor de sarcină nulă a suprafeţelor, majorarea intensităţii câmpului electric interior de accelerare, doparea unei părţi de nanocristale cu stibiu, micşorarea lucrului de ieşire a electronilor din aliajul de lipit pe bază de cositor cu 0,163 eV prin doparea acestuia cu stibiu, majorarea suprafeţei de contact a nanocristalelor de siliciu cu metalele anodului şi catodului, reducerea rezistenţei de contact la limitele de separare a aliajului şi suprafeţelor nanocristalelor, crearea unui câmp electric interior în stratul semiconductor, care accelerează sarcinile libere, utilizarea aliajelor galvanice, care asigură rezistenţa legăturii cu nanocristalele de siliciu, suprafeţele cărora posedă un potenţial majorat de sarcină nulă şi valori majorate ale lucrului de ieşire a electronilor până la 4,72 eV. The proposed invention allows: increasing the internal electromotive force between the electrodes by moving the anodic own potential towards the electropositive side and the cathodic one - towards the electronegative side, increasing the maximum possible current of the semiconductor converter by orienting the silicon nanocrystals in an external electrostatic field, increasing the potential difference between the anode and cathode by using galvanic alloys with high values of the zero charge potentials of the surfaces, increasing the intensity of the internal accelerating electric field, doping a part of the nanocrystals with staium, reducing the output work of electrons from the tin-based soldering alloy by 0.163 eV by doping it with antimony, increasing the contact surface of silicon nanocrystals with the anode and cathode metals, reducing the contact resistance at the separation limits of the alloy and nanocrystal surfaces, creating an internal electric field in the semiconductor layer, which accelerates free charges , the use of galvanic alloys, which ensure the strength of the bond with the silicon nanocrystals, the surfaces of which possess an increased potential of zero charge and increased values of the electron output work up to 4.72 eV.
Exemplu Example
Pentru testări în laborator au fost fabricate câte un convertor fotovoltaic: unul - conform invenţiei, altul - conform celei mai apropiate soluţii. For testing in the laboratory, one photovoltaic converter was manufactured: one - according to the invention, another - according to the closest solution.
Pentru fabricarea convertorului fotovoltaic a fost utilizat un cadru demontabil pătrat din oţel, dimensiunea unei laturi interioare a căruia a fost de 100 mm. Pe două laturi opuse ale cadrului din interior au fost fixate două rânduri de suporturi. Pe rândul de suporturi de sus a fost instalată o sticlă de cuarţ cu grosimea de 3 mm, iar pe rândul de jos - un aparat de topire, alimentat de la un transformator de laborator. Partea exterioară a cadrului (în partea de mijloc a acestuia) a fost fixată rigid de un suport cu posibilitatea rotirii cadrului pentru stabilirea poziţiei orizontale necesare a sticlei de cuarţ cu ajutorul unui nivelmetru. A square demountable steel frame was used for the manufacture of the photovoltaic converter, the size of an inner side of which was 100 mm. Two rows of supports were fixed on two opposite sides of the inner frame. A 3 mm thick quartz glass was installed on the top row of supports, and on the bottom row - a melting device, powered by a laboratory transformer. The outer part of the frame (in its middle part) was fixed rigidly to a support with the possibility of rotating the frame to establish the necessary horizontal position of the quartz glass with the help of a level meter.
Pe sticla de cuarţ a fost plasată o peliculă din aliaj de lipit pe bază de cositor (cositor-plumb) cu o grosime de 150 µm aliată cu stibiu în cantitate de 4% din masa aliajului. Pe suprafaţa peliculei a fost turnat un strat de nanocristale de siliciu cu dimensiuni de cca 40 nm, grosimea acestui strat a fost de 3…4 mm. Din partea cealaltă a cadrului (opusă suportului) a fost instalat un alt suport, de capătul liber al căruia a fost fixat un lagăr de alunecare din oţel, cu o bară verticală din ceramică cu dimensiuni de 15×50×120 mm. De părţile superioară şi inferioare ale barei simetric faţă de axa de rotaţie au fost fixate orizontal două plăci izolate cu dimensiuni de 110×125 mm. Una din plăci a fost conectată la polul pozitiv al unui potenţiostat, iar a doua - la polul negativ. Tensiunea aplicată a fost reglată de la 110 până la 240 V de la autotransformatorul de laborator. De suportul fix a fost fixat un raportor, iar de bara mobilă - un indicator al unghiului de rotaţie. On the quartz glass was placed a tin-based soldering alloy film (tin-lead) with a thickness of 150 µm alloyed with antimony in a quantity of 4% of the alloy mass. A layer of silicon nanocrystals with dimensions of about 40 nm was cast on the surface of the film, the thickness of this layer was 3...4 mm. On the other side of the frame (opposite to the support) another support was installed, to the free end of which a steel sliding bearing was fixed, with a ceramic vertical bar with dimensions of 15×50×120 mm. Two 110×125 mm insulated plates were fixed horizontally to the upper and lower parts of the bar symmetrically with respect to the axis of rotation. One of the plates was connected to the positive pole of a potentiostat, and the second - to the negative pole. The applied voltage was regulated from 110 to 240 V from the laboratory autotransformer. A protractor was attached to the fixed support, and an indicator of the rotation angle to the movable bar.
Deasupra cadrului cu nanocristale de siliciu a fost amplasată placa, conectată la polul pozitiv, iar sub cadru - placa, conectată la polul negativ, cu respectarea aliniamentului. De la reflectorul unei lămpi cu putere de 12 W, raza de lumină a fost direcţionată pe nanocristalele de siliciu cu intensitatea constantă. Pelicula din aliajul de lipit a fost conectată în serie printr-un conductor din cupru flexibil cu un rezistor de 10 Ω şi cu un mili- sau microampermetru, conectat la o grilă-catod portabilă, executată în formă de un şablon conductor de curent. Above the frame with silicon nanocrystals was placed the plate, connected to the positive pole, and below the frame - the plate, connected to the negative pole, respecting the alignment. From the reflector of a 12 W lamp, the light beam was directed onto the silicon nanocrystals with constant intensity. The solder alloy film was connected in series through a flexible copper conductor with a 10 Ω resistor and a milli- or microammeter, connected to a portable cathode-grid, made in the form of a current-conducting template.
Pentru identificarea poziţiei nanocristalelor, în care curentul din circuitul interior este maxim, sursa de câmp electrostatic exterior, şi respectiv câmpul electrostatic exterior cu intensitatea constantă se roteşte în jurul stratului semiconductor cu pasul de rotire de 10°. Fixarea valorii curentului a fost efectuată în momentul stabilirii contactelor şablonului cu nanocristalele de siliciu. To identify the position of the nanocrystals, where the current in the inner circuit is maximum, the external electrostatic field source, and respectively the external electrostatic field with constant intensity, is rotated around the semiconductor layer with a rotation step of 10°. The fixation of the current value was carried out at the moment of establishing the contacts of the template with the silicon nanocrystals.
La stabilirea curentului maxim în circuitul exterior, a fost determinată valoarea finală a unghiului între axa verticală şi indicatorul unghiului de rotaţie, îndreptat în direcţie opusă vectorului intensităţii câmpului electrostatic. După determinarea unghiului egal cu 40…50°, pelicula din aliaj de lipit, plasată orizontal pe sticla de cuarţ, a fost topită, în aliaj s-au depus nanocristalele de siliciu orientate, după care aliajul s-a răcit. A fost obţinută o placă cu grosimea de cca 280 µm, cu grosimea totală de 2 mm. When establishing the maximum current in the external circuit, the final value of the angle between the vertical axis and the rotation angle indicator, directed in the opposite direction to the electrostatic field intensity vector, was determined. After determining the angle equal to 40...50°, the solder alloy film, placed horizontally on the quartz glass, was melted, oriented silicon nanocrystals were deposited in the alloy, after which the alloy cooled. A plate with a thickness of approx. 280 µm was obtained, with a total thickness of 2 mm.
Suprafaţa posterioară a plăcii obţinute a fost acoperită cu adezivul organosilicic şi uscată. Pe suprafaţa frontală galvanic din electrolitul, care conţinea 360 g/L de FeCl2 şi 40 g/L de CoSO4 cu pH = 1,2, a fost depus un aliaj din fier-cobalt. În procesul electrochimic a fost aplicat un curent cu impuls de retur reglabil după amplitudine şi după durată (vezi SU 944031 A1 1982.07.15). Înainte de depunere a fost efectuată tratarea anodică a suprafeţei frontale a stratului semiconductor în decurs de 20 s la densitatea curentului de 60 A/dm2 cu impuls de retur deconectat. De suprafaţa frontală curăţită de oxizi şi de impurităţi a plăcii obţinute a fost fixat un şablon. În decurs de 3 min a fost mărită densitatea impulsului direct de la 0 până la 40 A/dm2 (ieşirea în regimul de lucru) şi prin şablon a fost efectuată depunerea catodică a aliajului în decurs de 20 min la raportul amplitudinilor impulsului catodic şi celui anodic de curent egal cu 6:1, densitatea catodică a curentului de 42…45 A/dm3 şi temperatura electrolitului de 313K. Grosimea stratului depus a fost de 180…190 µm. După finalizarea procesului de depunere a aliajului, convertorul fotovoltaic obţinut a fost spălat cu apă distilată curgătoare şi uscat într-o cameră la temperatura de 333K, după care a fost supus încercărilor: fără sarcină şi cu sarcină de 10 Ω. Convertorul fotovoltaic obţinut a fost cufundat în adeziv organosilicic în decurs de 90 s, înlăturat din vasul cu adeziv şi uscat în dulapul de uscat la temperatura de 360K timp de 10 min. The back surface of the plate obtained was covered with the organosilicon adhesive and dried. An iron-cobalt alloy was deposited on the galvanic front surface of the electrolyte, which contained 360 g/L of FeCl2 and 40 g/L of CoSO4 with pH = 1.2. In the electrochemical process, a return pulse current adjustable by amplitude and duration was applied (see SU 944031 A1 1982.07.15). Before the deposition, the anodic treatment of the front surface of the semiconductor layer was performed within 20 s at the current density of 60 A/dm2 with the return pulse disconnected. A template was attached to the front surface cleaned of oxides and impurities of the plate obtained. Within 3 min the density of the direct pulse was increased from 0 to 40 A/dm2 (the output in the working regime) and the cathodic deposition of the alloy was performed through the template within 20 min at the ratio of the cathodic and anodic pulse amplitudes of current equal to 6:1, the cathodic current density of 42...45 A/dm3 and the electrolyte temperature of 313K. The thickness of the deposited layer was 180...190 µm. After completing the alloy deposition process, the obtained photovoltaic converter was washed with running distilled water and dried in a room at a temperature of 333K, after which it was subjected to tests: without load and with a load of 10 Ω. The photovoltaic converter obtained was immersed in organosilicon adhesive within 90 s, removed from the adhesive pot and dried in the drying cabinet at a temperature of 360K for 10 min.
Încercări comparative ale convertoarelor fotovoltaice semiconductoare au fost realizate la iradierea cu radiaţie ionizantă solară. Comparative tests of semiconductor photovoltaic converters were carried out during irradiation with solar ionizing radiation.
Rezultatele testării au arătat că puterea specifică a convertorului fotovoltaic revendicat depăşeşte puterea specifică conform celei mai apropiate soluţii cu sticlă de protecţie de 2,4 ori, iar fără sticlă de protecţie - de 1,7 ori. The test results showed that the specific power of the claimed photovoltaic converter exceeds the specific power according to the closest solution with protective glass by 2.4 times, and without protective glass - by 1.7 times.
1. RU 2227343 C2 2004.04.20 1. RU 2227343 C2 2004.04.20
2. RU 2303830 C2 2007.07.27 2. RU 2303830 C2 2007.07.27
3. RU 2144718 C1 2000.01.20 3. RU 2144718 C1 2000.01.20
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| MD20100068A2 (en) | 2011-11-30 |
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