CN110444611A - A kind of solar battery and preparation method thereof of oxide passivation contact - Google Patents
A kind of solar battery and preparation method thereof of oxide passivation contact Download PDFInfo
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- 238000002161 passivation Methods 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 51
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 51
- 239000010703 silicon Substances 0.000 claims abstract description 51
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 39
- 238000000034 method Methods 0.000 claims abstract description 28
- 239000010408 film Substances 0.000 claims abstract description 25
- 239000011777 magnesium Substances 0.000 claims abstract description 24
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 23
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910052814 silicon oxide Inorganic materials 0.000 claims abstract description 20
- 238000001755 magnetron sputter deposition Methods 0.000 claims abstract description 16
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 14
- 238000000137 annealing Methods 0.000 claims abstract description 13
- 229910021419 crystalline silicon Inorganic materials 0.000 claims abstract description 12
- 239000010409 thin film Substances 0.000 claims abstract description 11
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052709 silver Inorganic materials 0.000 claims abstract description 7
- 239000004332 silver Substances 0.000 claims abstract description 7
- 229910052751 metal Inorganic materials 0.000 claims abstract description 5
- 239000002184 metal Substances 0.000 claims abstract description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 24
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 18
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 18
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 17
- 238000004544 sputter deposition Methods 0.000 claims description 17
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 14
- 239000001301 oxygen Substances 0.000 claims description 14
- 229910052760 oxygen Inorganic materials 0.000 claims description 14
- 239000013078 crystal Substances 0.000 claims description 13
- 229910052786 argon Inorganic materials 0.000 claims description 12
- 239000007789 gas Substances 0.000 claims description 12
- 238000004140 cleaning Methods 0.000 claims description 11
- 239000000377 silicon dioxide Substances 0.000 claims description 11
- 239000011259 mixed solution Substances 0.000 claims description 9
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 6
- 229910052774 Proactinium Inorganic materials 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 238000001552 radio frequency sputter deposition Methods 0.000 claims description 6
- 239000011224 oxide ceramic Substances 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 5
- 239000000395 magnesium oxide Substances 0.000 claims description 4
- 229910005855 NiOx Inorganic materials 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 229910052909 inorganic silicate Inorganic materials 0.000 claims description 3
- 239000005416 organic matter Substances 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- 238000005498 polishing Methods 0.000 claims description 3
- 238000012545 processing Methods 0.000 claims description 3
- 238000005477 sputtering target Methods 0.000 claims description 3
- 239000013077 target material Substances 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims 1
- 239000000919 ceramic Substances 0.000 claims 1
- 230000000149 penetrating effect Effects 0.000 claims 1
- 239000010936 titanium Substances 0.000 claims 1
- 229910052719 titanium Inorganic materials 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 6
- 229910003087 TiOx Inorganic materials 0.000 abstract description 2
- 238000005229 chemical vapour deposition Methods 0.000 abstract description 2
- 238000000151 deposition Methods 0.000 abstract description 2
- 230000008021 deposition Effects 0.000 abstract description 2
- 229910017604 nitric acid Inorganic materials 0.000 abstract description 2
- 238000000231 atomic layer deposition Methods 0.000 abstract 2
- HLLICFJUWSZHRJ-UHFFFAOYSA-N tioxidazole Chemical compound CCCOC1=CC=C2N=C(NC(=O)OC)SC2=C1 HLLICFJUWSZHRJ-UHFFFAOYSA-N 0.000 abstract 1
- 239000000463 material Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- 230000007547 defect Effects 0.000 description 4
- 230000005525 hole transport Effects 0.000 description 4
- 238000012546 transfer Methods 0.000 description 3
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 229910021417 amorphous silicon Inorganic materials 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- XJHCXCQVJFPJIK-UHFFFAOYSA-M caesium fluoride Chemical compound [F-].[Cs+] XJHCXCQVJFPJIK-UHFFFAOYSA-M 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 229910001930 tungsten oxide Inorganic materials 0.000 description 2
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- 229910000632 Alusil Inorganic materials 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229920000144 PEDOT:PSS Polymers 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 230000003667 anti-reflective effect Effects 0.000 description 1
- 229910000085 borane Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 235000008216 herbs Nutrition 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 1
- 230000010181 polygamy Effects 0.000 description 1
- 239000011970 polystyrene sulfonate Substances 0.000 description 1
- 229960002796 polystyrene sulfonate Drugs 0.000 description 1
- 239000005297 pyrex Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 231100000004 severe toxicity Toxicity 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 239000012780 transparent material Substances 0.000 description 1
- UORVGPXVDQYIDP-UHFFFAOYSA-N trihydridoboron Substances B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0216—Coatings
- H01L31/02161—Coatings for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/02167—Coatings for devices characterised by at least one potential jump barrier or surface barrier for solar cells
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/186—Particular post-treatment for the devices, e.g. annealing, impurity gettering, short-circuit elimination, recrystallisation
- H01L31/1868—Passivation
-
- 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
Abstract
The invention discloses a kind of solar batteries and preparation method thereof of oxide passivation contact, and battery has following structure: Ag/ITO/NiO from top to bottomx:Mg/SiOx/n‑c‑Si/SiOx/TiOx/Ag.When preparation, cleaned silicon wafer is put into HNO3Solution carries out thermal oxide growth, grows magnesium Y-oxides doping film using magnetron sputtering method, grows thin film of titanium oxide using magnetron sputtering method；Using laserscribing silicon wafer divided area be 1.5 × 1.5cm2Sample, then utilize magnetron sputtering method growth transparent conductive film and metal silver electrode；The battery to complete naturally cools to room temperature after annealing.The present invention does not need the film deposition equipment using the valuableness such as plasma activated chemical vapour deposition (PECVD) or atomic layer deposition (ALD), has the characteristics that simple process, at low cost, environmentally friendly.
Description
Technical field
The invention belongs to technical field of solar batteries, in particular to the solar battery of a kind of oxide passivation contact and
Preparation method.
Background technique
The main product of photovoltaic market is crystal silicon solar energy battery at present, its working principle is that using being entrained in silicon wafer
P-n junction is formed, since there are built in fields in p-n junction, the photo-generated carrier (electron-hole pair) that illumination generates is in built in field
Under the action of separate, electronics toward the area n direction move, hole toward the area p direction move, finally by silicon chip surface two electrodes receive
Collection.The critical process of the doping process crystal silicon cell of silicon wafer usually carries out under high temperature (800~1000 DEG C), doping
It needs to remove the silicon chip surface after High temperature diffusion afterwards and forms phosphorosilicate glass or Pyrex.Doping increases answering for battery process
Polygamy also increases cost, while when silicon wafer thickness is further thinned to 100 μm or less, due to the heat of back side alusil alloy
Coefficient of expansion difference is very big, and high temperature when diffusion can make silicon wafer generate very big bending, seriously affects the formation of Al-BSF, causes
The series resistance of battery is larger, to reduce the efficiency of battery.
In recent years, undoped heterojunction solar battery becomes heat studied both at home and abroad at present since preparation method is simple
Point, this battery are by admixture or structure come bending energy band, and possess good surface passivation effect and can be efficient
A kind of carrier is transmitted, carrier is selectively passed through and collected to realize, this has with the battery by diffuseing to form p-n junction
Essence difference.It is inserted into one layer of passivation contact material formation passivation between crystalline silicon and metal electrode to contact, there is passivation
With contact function, the Carrier recombination of silicon face can be lowered, at the same can efficiently transport again a kind of type of carrier (electronics or
Hole) and another type of carrier is prevented, realize efficiently separating and finally being collected by external two electrodes for photo-generated carrier
Function.Compared with traditional p-n junction battery, carrier selective exposure solar battery is due to excellent surface passivation
Effect can make battery obtain higher transfer efficiency, simultaneously because do not need to adulterate, can simplify battery preparation process and
Low temperature preparation is realized, to reduce the production cost of battery.
In organic solar batteries, organic material (such as poly- 3,4-rthylene dioxythiophene/poly styrene sulfonate,
PEDOT:PSS), transition metal oxide (such as molybdenum oxide, tungsten oxide, vanadium oxide) is utilized as hole transport layer material,
Lithium fluoride, cesium fluoride etc. are used as electron transport layer materials.For undoped passivation contact crystalline silicon battery, passivation contact
Material is in addition to having the function of transmitting electronics or hole, it is necessary to have good deactivation function to crystalline silicon.Above-mentioned electronics
Or hole transport layer material is not very good to the passivation effect of silicon, if being inserted into one layer between these materials and crystal silicon body
Amorphous silicon or ultra-thin silica, then passivation effect can significantly increase, such as HIT (hetero-junctions of amorphous silicon intrinsic thin layer) and TOPCon
(tunnel oxide passivation contact) battery.The preparation of HIT and TOPCon battery need silane, phosphine, borine etc. inflammable and explosive and
The reaction gas of severe toxicity, and TOPCon battery also needs the high temperature anneal, therefore exploitation is environmentally friendly, preparation process is simple
Single, low-cost non-impurity-doped crystal silicon solar energy battery is of great significance.
Summary of the invention
The object of the present invention is to provide the solar batteries of a kind of low cost, simple process, and provide preparation method.
It is a kind of to can applicants have found that nickel oxide is a kind of broad-band gap (3.6~4.0eV) oxide semiconductor
Light-exposed transparent material.For the work function (4.3~5.0eV) of crystalline silicon, nickel oxide high work function with higher
(5.2~6.0eV), when it constitutes hetero-junctions with silicon, valence band offset easy to form plays the role of stopping electron-transport, right
It is very suitable hole transport layer material for silicon.Nickel oxide (NiO) with complete stoichiometric ratio is insulating materials, electricity
Resistance rate is up to 1013Ω .cm, however due to usually there is a large amount of nickel vacancy in film, lead to the nickel oxide of non-stoichiometric
(NiOx) resistivity sharply decline, but still be maintained at 102~105Ω .cm magnitude.In order to reduce its resistivity, usually to it
Carry out the doping of metal ion.Closely due to magnesium ion radius (0.272nm) and nickel ion radius (0.269nm),
Magnesium adulterates the distortion for hardly causing nickel oxide lattice.For example, using the nickel Y-oxides doping resistivity of Grown by Magnetron Sputtering
Usually 0.1~100 Ω .cm.In addition, the band gap width that magnesia has is more much bigger than nickel oxide, therefore mix the nickel oxide of magnesium
It can also be improved the light transmittance of film.
When titanium oxide and silicon constitute hetero-junctions, conduction band offset easy to form plays the role of stopping hole transport, for silicon
For be very suitable electron transport layer materials.Using the titanium oxide of Grown by Magnetron Sputtering, there are a large amount of Lacking oxygens, lead to its
Resistivity is smaller, and representative value is 0.05~1.0 Ω .cm.Since the nickel oxide and thin film of titanium oxide of Grown by Magnetron Sputtering are to crystal
The passivation effect of silicon face is not fine, therefore is inserted into one layer of ultra-thin silica between them, can be both passivated well
Silicon face, carrier can be tunneled through again.After low-temperature annealing, interface quality is greatly improved.
Based on above-mentioned thinking, the technical solution adopted by the present invention is that such: a kind of solar energy of oxide passivation contact
Battery has following structure: Ag/ITO/NiO from top to bottomx:Mg/SiOx/n-c-Si/SiOx/TiOx/Ag。
The present invention also uses such technical solution: a kind of preparation method of the solar battery of oxide passivation contact,
The following steps are included:
1) cleaning silicon chip:
N-shaped twin polishing pulling of crystals silicon wafer is taken, is 0.2~1.0 Ω .cm with a thickness of 180~220 μm, resistivity；Silicon wafer
Cleaning step is as follows:
A) with acetone remove surface organic matter, 25 DEG C of temperature, time 10min；
B) sulfuric acid and hydrogen peroxide mixed solution (H are used2SiO4:H2O2=3:1) removal native oxide, while carrying out chemistry
The growth of oxide layer, 75 DEG C of temperature, time 15min；
C) hydrofluoric acid and hydrochloric acid mixed solution (HF:HCl:H are used2O=1:1:15 removing oxide layer, room temperature, time 2min) are removed；
D) hydrochloric acid and hydrogen peroxide mixed solution (HCl:H are used2O2:H2O=1:1:4 oxide layer, room temperature, time) are grown
15min；
E) dilute HF acid aqueous solution (HF:H is used2O=1:50 removing oxide layer, room temperature, time 30s) are removed；Silicon after cleaning
Piece carries out the growth of silica immediately, or is transferred in vacuum box and saves；
2) silica (SiOx) growth:
Cleaned silicon wafer is put into the HNO that temperature is 115 DEG C, concentration is 63wt%3Solution carries out thermal oxide growth, when
Between be 10min；
3) magnesium Y-oxides doping (NiOx: Mg) film growth:
Magnesium Y-oxides doping film is grown using magnetron sputtering method, with a thickness of 10nm, specific growth technique is as follows: magnesium is mixed
Miscellaneous nickel oxide ceramic target is made of nickel oxide and magnesia, and the content of nickel oxide is 2.3~4.3wt%.Sputtering chamber background
Vacuum is better than 5 × 10-4Pa, rf sputtering power be 20~30W, rf frequency 13.56MHz, sputtering pressure be 0.5~
2.0Pa, sputtering working gas are argon gas and oxygen, and argon flow 30sccm, oxygen is 0.7~1.3sccm, and underlayer temperature is
220℃；
4) titanium oxide (TiOx) film growth:
Thin film of titanium oxide is grown using magnetron sputtering method, with a thickness of 10nm, specific growth technique is as follows: sputtering target material is
Titanium oxide ceramics target, sputtering chamber base vacuum are better than 5 × 10-4Pa, rf sputtering power are 20~30W, and rf frequency is
13.56MHz, sputtering pressure are 0.5~2.0Pa, and sputtering working gas is argon gas and oxygen, argon flow 30sccm, oxygen
For 0.5~0.8sccm, underlayer temperature is 220 DEG C；
5) ito thin film and silver electrode growth and low-temperature annealing processing:
Using laserscribing silicon wafer divided area be 1.5 × 1.5cm2Sample, then utilize magnetron sputtering method
Transparent conductive film and metal silver electrode are grown, growth temperature is 200 DEG C；Firstly, successively in front side of silicon wafer growth thickness
Then the ito thin film of 70nm sputters one layer of fourchette shape, the Ag electrode with a thickness of 500nm using mask plate on positive ITO, with
The Ag electrode with a thickness of 500nm is sputtered on reverse side ITO afterwards；The battery to complete is in air at a temperature of 250~300 DEG C
Anneal 30min, naturally cools to room temperature after annealing.
The present invention grows the nickel oxide (NiO of magnesium doping by magnetron sputtering methodx: Mg) and titanium oxide (TiOx) and nitric acid
Thermal oxidation method grows ultra-thin silica (SiOx), using NiOx:Mg/SiOxHole as N-shaped monocrystalline silicon (n-c-Si) selects
Property passivation contact layer, TiOx/SiOxElectronic selection as n-c-Si is passivated contact layer.Hole and electronic selection passivation connect
Touching is after low-temperature annealing, NiOxAnd TiOxIn oxygen pass through SiOxIt is diffused into SiOxThe interface /n-c-Si, leads to the defect at interface
Density reduces, simultaneously because the filling of Lacking oxygen is so that SiOxFixed charge density also reduce, enhance the passivation of silicon face
Effect, to improve the transfer efficiency of battery.The present invention is not needed using plasma activated chemical vapour deposition (PECVD) or original
Sublayer deposits the expensive film deposition equipment such as (ALD), has the characteristics that simple process, at low cost, environmentally friendly.
Detailed description of the invention
It is described in further detail below in conjunction with attached drawing and embodiments of the present invention
Fig. 1 is battery structure schematic diagram of the invention.
Specific embodiment
Referring to attached drawing.Battery described in the present embodiment from top to bottom, has following structure: Ag electrode 1, ito thin film 2
(70nm), NiOx:Mg film 3 (10nm), SiOx layer 4 (1.4nm), n-c-Si layer 5, SiOx layer 4 (1.4nm), TiOx film 6
(10nm), Ag electrode 1.
When preparation:
1. Wafer Cleaning
The non-doped crystal silicon solar cell that the oxide passivation of the present embodiment design connects, in order to reduce silicon chip surface
Impurity concentration reduces the boundary defect density of states between silicon chip surface and passivation layer, therefore requires very silicon wafer surface cleaning
Height, while the cleaning of silicon wafer is also very crucial to the growth of subsequent ultra-thin silica.
The silicon wafer of experiment is N-shaped twin polishing pulling of crystals silicon wafer, with a thickness of 180~220 μm, resistivity be 0.2~
1.0Ω.cm.Steps are as follows for Wafer Cleaning:
A) with acetone remove surface organic matter, 25 DEG C of temperature, time 10min；
B) sulfuric acid and hydrogen peroxide mixed solution (H are used2SiO4:H2O2=3:1) removal native oxide, while carrying out chemistry
The growth of oxide layer, 75 DEG C of temperature, time 15min；
C) hydrofluoric acid and hydrochloric acid mixed solution (HF:HCl:H are used2O=1:1:15 removing oxide layer, room temperature, time 2min) are removed；
D) hydrochloric acid and hydrogen peroxide mixed solution (HCl:H are used2O2:H2O=1:1:4 oxide layer, room temperature, time) are grown
15min；
E) dilute HF acid aqueous solution (HF:H is used2O=1:50 removing oxide layer, room temperature, time 30s) are removed；
F) silicon wafer after cleaning carries out the growth of silica immediately, or is transferred in vacuum box and saves.
2. silica (SiOx) growth
In order to further decrease the defect state density of silicon face, ultra-thin silica is grown using wet chemical oxidation method and is carried out
Passivation.Cleaned silicon wafer is put into the HNO that temperature is 115 DEG C, concentration is 63wt%3Solution carries out thermal oxide growth, time
It is about 1.4nm in the silicon oxide thickness that silicon wafer tow sides obtain for 10min.
3. magnesium Y-oxides doping (NiOx: Mg) film growth
Magnesium Y-oxides doping film is grown using magnetron sputtering method, with a thickness of 10nm, specific growth technique is as follows.Magnesium is mixed
Miscellaneous nickel oxide ceramic target is made of nickel oxide and magnesia, and the content of nickel oxide is 2.3~4.3wt%.Sputtering chamber background
Vacuum is better than 5 × 10-4Pa, rf sputtering power be 20~30W, rf frequency 13.56MHz, sputtering pressure be 0.5~
2.0Pa, sputtering working gas are argon gas and oxygen, and argon flow 30sccm, oxygen is 0.7~1.3sccm, and underlayer temperature is
220 DEG C, film thickness vibrates monitoring by quartz crystal.By electrical measurement, the resistivity of rear film of annealing is 13~
65mΩ.cm。
4. titanium oxide (TiOx) film growth
Thin film of titanium oxide is grown using magnetron sputtering method, with a thickness of 10nm, specific growth technique is as follows.Sputtering target material is
Titanium oxide ceramics target, sputtering chamber base vacuum are better than 5 × 10-4Pa, rf sputtering power are 20~30W, and rf frequency is
13.56MHz, sputtering pressure are 0.5~2.0Pa, and sputtering working gas is argon gas and oxygen, argon flow 30sccm, oxygen
For 0.5~0.8sccm, underlayer temperature is 220 DEG C, and film thickness vibrates monitoring by quartz crystal.By electrical measurement,
The resistivity of annealing rear film is 1.5~6.4m Ω .cm.
5.ITO film and silver electrode growth and low-temperature annealing processing
Using laserscribing silicon wafer divided area be 1.5 × 1.5cm2Sample, then utilize magnetron sputtering method
Transparent conductive film and metal silver electrode are grown, growth temperature is 200 DEG C.Firstly, successively in front side of silicon wafer growth thickness
Then the ito thin film of 70nm sputters one layer of fourchette shape, the Ag electrode with a thickness of 500nm using mask plate on positive ITO, with
The Ag electrode with a thickness of 500nm is sputtered on reverse side ITO afterwards.The battery to complete is in air at a temperature of 250~300 DEG C
Anneal 30min, naturally cools to room temperature after annealing.
6. cell photoelectric performance test
In AM1.5,100mW/cm2, under 25 DEG C of standard test condition, structure Ag/ITO/NiOx:Mg/SiOx/n-c-
Si/SiOx/TiOx/ Ag battery is as shown in table 1 in the performance for stepping back front and back:
Performance of 1 battery of table before and after annealing
From table 1 it follows that the annealing after the completion of battery preparation, can increase battery performance, crystalline silicon really
The passivation quality of front and rear surfaces is largely increased, and the open-circuit voltage of battery increases to 0.523V from 0.406V, transfer efficiency from
6.72% increases to 10.2%.The improvement of this battery performance is mainly due to the reduction of interface defect density, reduces interface
The fermi level pinning of state enhances the effect of built in field.Although magnesium Y-oxides doping and the titanium oxide passivation prepared at present
The efficiency of the non-impurity-doped crystal silicon solar energy battery of contact or relatively low, this is because there are also excellent for each section parameter of battery
Change, for example, silicon chip surface making herbs into wool, anti-reflective layer etc. optimization design.Nevertheless, tungsten oxide passivation contact proposed by the present invention
Non-doped crystal silicon solar cell mentality of designing, to realize that preparation process is simple, high efficiency crystalline of low production cost
Silicon solar cell provides referential directive significance.
Claims (2)
1. a kind of solar battery of oxide passivation contact, it is characterised in that: have following structure: Ag/ from top to bottom
ITO/NiOx:Mg/SiOx/n-c-Si/SiOx/TiOx/Ag。
2. a kind of preparation method of solar battery described in claim 1, it is characterised in that: the following steps are included:
1) cleaning silicon chip:
N-shaped twin polishing pulling of crystals silicon wafer is taken, is 0.2~1.0 Ω .cm with a thickness of 180~220 μm, resistivity；Wafer Cleaning
Steps are as follows:
A) with acetone remove surface organic matter, 25 DEG C of temperature, time 10min；
B) sulfuric acid and hydrogen peroxide mixed solution (H are used2SiO4:H2O2=3:1) removal native oxide, while carrying out chemical oxide layer
Growth, 75 DEG C of temperature, time 15min；
C) hydrofluoric acid and hydrochloric acid mixed solution (HF:HCl:H are used2O=1:1:15 removing oxide layer, room temperature, time 2min) are removed；
D) hydrochloric acid and hydrogen peroxide mixed solution (HCl:H are used2O2:H2O=1:1:4 oxide layer, room temperature, time 15min) are grown；
E) dilute HF acid aqueous solution (HF:H is used2O=1:50 removing oxide layer, room temperature, time 30s) are removed；Silicon wafer after cleaning is immediately
The growth of silica is carried out, or is transferred in vacuum box and saves；
2) silica (SiOx) growth:
Cleaned silicon wafer is put into the HNO that temperature is 115 DEG C, concentration is 63wt%3Solution carries out thermal oxide growth, and the time is
10min；
3) magnesium Y-oxides doping (NiOx: Mg) film growth:
Magnesium Y-oxides doping film is grown using magnetron sputtering method, with a thickness of 10nm, specific growth technique is as follows: magnesium doping
Nickel oxide ceramic target is made of nickel oxide and magnesia, and the content of nickel oxide is 2.3~4.3wt%.Sputtering chamber base vacuum
Better than 5 × 10-4Pa, rf sputtering power are 20~30W, and rf frequency 13.56MHz, sputtering pressure is 0.5~2.0Pa, is splashed
Penetrating working gas is argon gas and oxygen, and argon flow 30sccm, oxygen is 0.7~1.3sccm, and underlayer temperature is 220 DEG C；
4) titanium oxide (TiOx) film growth:
Grow thin film of titanium oxide using magnetron sputtering method, with a thickness of 10nm, specific growth technique is as follows: sputtering target material is oxidation
Titanium ceramic target, sputtering chamber base vacuum are better than 5 × 10-4Pa, rf sputtering power be 20~30W, rf frequency 13.56MHz,
Sputtering pressure be 0.5~2.0Pa, sputtering working gas be argon gas and oxygen, argon flow 30sccm, oxygen be 0.5~
0.8sccm, underlayer temperature are 220 DEG C；
5) ito thin film and silver electrode growth and low-temperature annealing processing:
Using laserscribing silicon wafer divided area be 1.5 × 1.5cm2Sample, then using magnetron sputtering method grow
Transparent conductive film and metal silver electrode, growth temperature are 200 DEG C；Firstly, successively front side of silicon wafer growth thickness 70nm's
Then ito thin film sputters one layer of fourchette shape, the Ag electrode with a thickness of 500nm using mask plate, then anti-on positive ITO
The Ag electrode with a thickness of 500nm is sputtered on the ITO of face；The battery to complete is annealed in air at a temperature of 250~300 DEG C
30min naturally cools to room temperature after annealing.
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| CN111584667A (en) * | 2020-06-09 | 2020-08-25 | 山西潞安太阳能科技有限责任公司 | Novel N-type crystalline silicon TOPCon battery structure and preparation process thereof |
| CN112509726A (en) * | 2020-12-01 | 2021-03-16 | 通威太阳能（成都）有限公司 | Boron-aluminum paste for back field doping, solar cell and preparation method thereof |
| CN113130670A (en) * | 2021-04-20 | 2021-07-16 | 浙江师范大学 | Europium oxide/platinum passivated contact crystalline silicon solar cell and preparation method thereof |
| CN113629162A (en) * | 2021-08-31 | 2021-11-09 | 晶澳（扬州）太阳能科技有限公司 | Silicon-based solar cell unit and manufacturing method thereof |
| CN114171641A (en) * | 2021-11-30 | 2022-03-11 | 北京燕东微电子科技有限公司 | Etching method of vanadium oxide film and manufacturing method of semiconductor device |
| CN115745418A (en) * | 2022-11-23 | 2023-03-07 | 中国科学院宁波材料技术与工程研究所 | Quick-response nickel oxide electrochromic film and preparation method and application thereof |
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| CN116454141A (en) * | 2023-04-20 | 2023-07-18 | 江苏海洋大学 | Transparent conductive passivation laminated film applied to crystalline silicon solar cell and preparation method thereof |
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| CN111584667A (en) * | 2020-06-09 | 2020-08-25 | 山西潞安太阳能科技有限责任公司 | Novel N-type crystalline silicon TOPCon battery structure and preparation process thereof |
| CN112509726A (en) * | 2020-12-01 | 2021-03-16 | 通威太阳能（成都）有限公司 | Boron-aluminum paste for back field doping, solar cell and preparation method thereof |
| CN113130670A (en) * | 2021-04-20 | 2021-07-16 | 浙江师范大学 | Europium oxide/platinum passivated contact crystalline silicon solar cell and preparation method thereof |
| CN113629162A (en) * | 2021-08-31 | 2021-11-09 | 晶澳（扬州）太阳能科技有限公司 | Silicon-based solar cell unit and manufacturing method thereof |
| WO2023087310A1 (en) * | 2021-11-22 | 2023-05-25 | 宁德时代新能源科技股份有限公司 | Method for forming hole transport layer on surface of substrate, and hole transport layer, solar cell and preparation method therefor, and photovoltaic module |
| CN114171641A (en) * | 2021-11-30 | 2022-03-11 | 北京燕东微电子科技有限公司 | Etching method of vanadium oxide film and manufacturing method of semiconductor device |
| CN115745418A (en) * | 2022-11-23 | 2023-03-07 | 中国科学院宁波材料技术与工程研究所 | Quick-response nickel oxide electrochromic film and preparation method and application thereof |
| CN116454141A (en) * | 2023-04-20 | 2023-07-18 | 江苏海洋大学 | Transparent conductive passivation laminated film applied to crystalline silicon solar cell and preparation method thereof |
| CN116454141B (en) * | 2023-04-20 | 2024-01-19 | 江苏海洋大学 | Transparent conductive passivation laminated film applied to crystalline silicon solar cell and preparation method thereof |
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