CN109037391A - A kind of cadmium stannate transparent conductive film, its production technology and solar battery - Google Patents
A kind of cadmium stannate transparent conductive film, its production technology and solar battery Download PDFInfo
- Publication number
- CN109037391A CN109037391A CN201710428907.1A CN201710428907A CN109037391A CN 109037391 A CN109037391 A CN 109037391A CN 201710428907 A CN201710428907 A CN 201710428907A CN 109037391 A CN109037391 A CN 109037391A
- Authority
- CN
- China
- Prior art keywords
- transparent conductive
- conductive film
- production technology
- cadmium stannate
- film
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229910052793 cadmium Inorganic materials 0.000 title claims abstract description 35
- 229940071182 stannate Drugs 0.000 title claims abstract description 35
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 30
- 238000005516 engineering process Methods 0.000 title claims abstract description 25
- 239000012298 atmosphere Substances 0.000 claims abstract description 37
- 230000001681 protective effect Effects 0.000 claims abstract description 28
- 238000001755 magnetron sputter deposition Methods 0.000 claims abstract description 21
- XOLBLPGZBRYERU-UHFFFAOYSA-N SnO2 Inorganic materials O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000007789 gas Substances 0.000 claims description 30
- 239000002243 precursor Substances 0.000 claims description 27
- 210000002469 basement membrane Anatomy 0.000 claims description 26
- 229910052760 oxygen Inorganic materials 0.000 claims description 22
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 20
- 239000001301 oxygen Substances 0.000 claims description 20
- 238000004544 sputter deposition Methods 0.000 claims description 20
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 18
- 229910052786 argon Inorganic materials 0.000 claims description 10
- 239000013077 target material Substances 0.000 claims description 6
- 229910000925 Cd alloy Inorganic materials 0.000 claims description 5
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 3
- 238000000137 annealing Methods 0.000 abstract description 49
- 238000002360 preparation method Methods 0.000 abstract description 25
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 10
- 238000000034 method Methods 0.000 abstract description 10
- 230000003287 optical effect Effects 0.000 abstract description 5
- 239000010408 film Substances 0.000 description 69
- 239000000758 substrate Substances 0.000 description 13
- 238000009738 saturating Methods 0.000 description 8
- MARUHZGHZWCEQU-UHFFFAOYSA-N 5-phenyl-2h-tetrazole Chemical compound C1=CC=CC=C1C1=NNN=N1 MARUHZGHZWCEQU-UHFFFAOYSA-N 0.000 description 7
- 238000000151 deposition Methods 0.000 description 7
- 230000008021 deposition Effects 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 238000012360 testing method Methods 0.000 description 5
- 239000011521 glass Substances 0.000 description 4
- 210000004379 membrane Anatomy 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 2
- UHYPYGJEEGLRJD-UHFFFAOYSA-N cadmium(2+);selenium(2-) Chemical compound [Se-2].[Cd+2] UHYPYGJEEGLRJD-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910004613 CdTe Inorganic materials 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000006059 cover glass Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 239000010409 thin film Substances 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
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/1884—Manufacture of transparent electrodes, e.g. TCO, ITO
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
-
- 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
- H01L31/0224—Electrodes
- H01L31/022408—Electrodes for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/022425—Electrodes for devices characterised by at least one potential jump barrier or surface barrier for solar cells
-
- 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
This application provides a kind of cadmium stannate transparent conductive film, its production technology and solar batteries.Target is first carried out to magnetron sputtering in the production technology of the application in mixed-gas environment, then is annealed under protective atmosphere.Production technology according to the invention; the preparation speed of CTO film can be obviously improved; be conducive to carry out large-scale production; more importantly; preparation method according to the invention is without carrying out abutting annealing way; it anneals directly under protective atmosphere, enormously simplifies annealing process, can be realized industrialization large-scale production.Solar battery the present invention also provides a kind of cadmium stannate transparent conductive film and comprising the cadmium stannate transparent conductive film, compared to existing commercialized SnO2The electrical and optical performance of film and ito film, cadmium stannate transparent conductive film provided by the invention significantly improves.
Description
Technical field
The present invention relates to technical field of solar batteries, in particular to a kind of cadmium stannate transparent conductive film, its production technology
And solar battery.
Background technique
Cadmium telluride (CdTe) thin-film solar cells is a kind of commercialized high performance solar batteries, and conventional structure is as schemed
Shown in 1, including substrate glass-TCO transparent conductive film-Window layer-CdTe absorbed layer-transition zone-Metal contact electrode, wherein
TCO transparent conductive film is the preceding electrode of solar battery, and effect is the carrier for generating semiconductor under sunlight irradiation
It is effectively collected, while reducing resistance bring energy loss itself.Under being due to conventional cadmium telluride class solar battery into
Photo structure needs more light to enter semiconductor absorption layer, converts it into electron hole to promote the utilization rate of sunlight
Right, so that luminous energy is converted to electric energy, this just needs such as TCO film layer of the film layer before semiconductor to lack extinction as far as possible, have compared with
High light transmittance reduces loss of the light before being incident on absorbed layer.
Currently, being commercialized common TCO transparent conductive film is SnO2Film and ito film, can laboratory preparation TCO conductive film
There is cadmium stannate (Cd2SnO4, abbreviation CTO) and film；CTO film can reach when film thickness is 170nm or less and SnO2Film and ito film phase
When surface resistance, having high carrier concentration 6.6 × 10 mainly due to CTO20cm-3While, also there is 53.2cm2/ Vs's
High mobility；Moreover, optical transmittance is in 400~800nm wave-length coverage when the square resistance of CTO film is lower than 3ohm/
Mean value can be more than 85%, be much higher than commercialized SnO2Film and ito film.High light transmittance makes more light be irradiated to absorption
Layer, increases the short circuit current of battery, to improve the photoelectric conversion efficiency of battery；Low resistance makes CTO be applied to solar-electricity
The series resistance that battery is reduced when pond improves the fill factor of battery, and then improves the photoelectric conversion efficiency of battery.CTO's is another
One characteristic is that have low surface roughness, roughness≤2nm smooth surface can be obtained, compared to commercialized SnO2Film drop
Low an order of magnitude, low roughness are conducive to improve short circuit current using thin Window layer, at the same reduce boundary defect and
Interface composites improve the open-circuit voltage of battery.In addition, the high-temperature stability of CTO is more excellent, its electrical property after high-temperature process
Can be there is no larger change, and SnO2Resistance significantly increases after the high temperature anneal, the high-temperature stability ratio SnO of ito film2
Film is worse；The preparation process of CdTe absorbed layer is high-temperature technology, the high-temperature stability of TCO film layer in cadmium telluride class solar battery
It is also particularly significant to cadmium telluride class solar battery.It can be seen that the comprehensive performance of CTO film is than current commercialized SnO2Film and
Ito film is obviously more preferable, is therefore the rare transparent conductive material suitable for cadmium telluride solar battery develops CTO's
Large-scale production is of great significance to this field.
However, magnetron sputtering is usually carried out under room temperature under total oxygen atmosphere, then when preparing CTO film in the prior art
Again in N2Under protection, and it is close to annealing with CdS film at 650 DEG C of even higher temperature and (is close to annealing and refers to that offer is deposited on
The CTO film of substrate, and it is deposited on the CdS film of substrate, the CTO film with substrate is faced with the CdS film with substrate
Face paste is closed, as shown in Fig. 2, annealing at high temperature again).However, in the preparation process, on the one hand, sputtering sedimentation CTO film
Speed it is slower, be not suitable for large-scale production；On the other hand, annealing generally requires to carry out at 650 DEG C of even higher temperature,
It has been more than the softening temperature of common glass substrate, has needed using special high temperature-resistant liner bottom, which considerably increases membrane material
Cost of manufacture, limit industrial scale production；Moreover, carrying out CdS film on substrate is close to annealing with CTO film surface opposite,
It is uneven to easily lead to CTO film there are when problem for substrate surface evenness；And therefore this kind face-to-face be close to annealing way be not appropriate for greatly
The inline process of scale automation can also greatly increase industry even if design additional machinery structure auxiliary film surface is close to annealing
Change the difficulty of mass automatic production.In addition, CdS film layer is used for multiple times, it is easy to stain impurity, to further pollute CTO
Film layer makes the performance of CTO fall flat, and also brings uncontrollable factor for the stability of technique.Therefore, the prior art
In, CTO film is often only able to achieve laboratory preparation and research, and is difficult to realize industrialization large-scale production.
Summary of the invention
In view of this, the purpose of the present invention is to provide a kind of cadmium stannate transparent conductive film, its production technology and solar energy
Battery.Production technology according to the invention can be obviously improved the preparation speed of CTO film, moreover, without carrying out being close to annealing side
Formula anneals directly under protective atmosphere, enormously simplifies annealing process, can be realized industrialization large-scale production.
The present invention provides a kind of production technologies of cadmium stannate transparent conductive film, comprising the following steps:
A) target is carried out in mixed-gas environment to magnetron sputtering, obtain precursor CTO basement membrane；
The target is by SnO2The target formed with CdO, or be Sn-Cd alloy target material；
The mixed gas be argon gas and oxygen, wherein oxygen account for the mixed gas volume fraction be 5%~
15%；
B) the precursor CTO basement membrane is annealed under protective atmosphere, obtains cadmium stannate transparent conductive film.
Preferably, in the step a), the air pressure of the mixed gas is 5~30mTorr.
Preferably, in the step a), the sputtering power of the magnetron sputtering is 460~600W.
Preferably, in the step a), the sputtering time of the magnetron sputtering is less than or equal to 10min.
Preferably, described by SnO in the step a)2In the target of CdO composition, SnO2Molar ratio with CdO is 1:
(1.9~2.1).
Preferably, in the step a), the flow of argon gas is 20~500sccm；The flow of oxygen is 1~100sccm.
Preferably, in the step b), the protective atmosphere is argon atmosphere or nitrogen atmosphere.
Preferably, the cadmium stannate transparent conductive film with a thickness of 150~500nm.
The present invention also provides cadmium stannate transparent conductive films made from the production technology described in above-mentioned technical proposal.
The present invention also provides a kind of solar battery, the TCO transparent conductive film in the solar battery is above-mentioned skill
Cadmium stannate transparent conductive film described in art scheme.
The present invention provides a kind of production technologies of cadmium stannate transparent conductive film, comprising the following steps: a) by target mixed
It closes in gaseous environment and carries out magnetron sputtering, obtain precursor CTO basement membrane；The target is by SnO2The target formed with CdO, or be
Sn-Cd alloy target material；The mixed gas is argon gas and oxygen, wherein the volume fraction that oxygen accounts for the mixed gas is 5%
~15%；B) the precursor CTO basement membrane is annealed under protective atmosphere, obtains cadmium stannate transparent conductive film.According to this
The production technology of invention can be obviously improved the preparation speed of CTO film, be conducive to carry out large-scale production, it is even more important that
Preparation method according to the invention is annealed directly under protective atmosphere, is enormously simplified without carrying out abutting annealing way
Annealing process can be realized industrialization large-scale production.The present invention also provides a kind of cadmium stannate transparent conductive film and include this
The solar battery of cadmium stannate transparent conductive film, compared to existing commercialization TCO film, cadmium stannate electrically conducting transparent provided by the invention
The electrical and optical performance of film significantly improves.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
The embodiment of invention for those of ordinary skill in the art without creative efforts, can also basis
The attached drawing of offer obtains other attached drawings.
Fig. 1 is the structure chart of existing solar battery；
Fig. 2 is existing abutting annealing way structure chart；
Fig. 3 is the saturating curve graph of light of sample segment in embodiment 2；
Fig. 4 is the resistivity effect picture of sample segment in embodiment 2；
Fig. 5 is the saturating curve graph of light of sample segment in embodiment 2；
Fig. 6 is the resistivity effect picture of sample segment in embodiment 2.
Specific embodiment
The present invention provides a kind of production technologies of cadmium stannate transparent conductive film, which comprises the following steps:
A) target is carried out in mixed-gas environment to magnetron sputtering, obtain precursor CTO basement membrane；
The target is by SnO2The target formed with CdO, or be Sn-Cd alloy target material；
The mixed gas be argon gas and oxygen, wherein oxygen account for the mixed gas mass fraction be 5%~
15%；
B) the precursor CTO basement membrane is annealed under protective atmosphere, obtains cadmium stannate transparent conductive film.
Production technology according to the invention prepares cadmium stannate transparent conductive film, has faster deposition velocity, moreover, moving back
It is close to annealing without carrying out CdS when fiery, anneals directly under protective atmosphere, enormously simplify annealing process, Neng Goushi
Existing industrialization large-scale production.
According to the present invention, target is carried out to magnetron sputtering in mixed-gas environment first, obtains precursor CTO basement membrane.
In the present invention, target selected by magnetron sputtering can be SnO2With target (the i.e. SnO of CdO composition2- CdO target
Material), or Sn-Cd alloy target material；Preferably SnO2- CdO target.In the present invention, the target is SnO2- CdO target
When, SnO2Molar ratio with CdO is preferably 1:(1.9~2.1), it can be specially 33:67 such as in some embodiments.
In the present invention, before carrying out magnetron sputtering, preferably sputtering chamber is vacuumized, vacuum degree is preferably≤2.5E-
6Torr。
After vacuumizing, it is passed through gas into sputtering chamber, in the present invention, magnetron sputtering carries out in mixed-gas environment, institute
Stating mixed gas is argon gas and oxygen；In the present invention, argon flow is preferably 20~500sccm；Oxygen flow is preferably 1~
100sccm.In the present invention, the volume fraction that oxygen accounts for the mixed gas is 5%~15%；As in some embodiments, mix
The volume ratio for closing oxygen in gas can be 10%.
In the present invention, magnetron sputtering is preferably carried out in the case where gas atmosphere is 5~30mTorr, such as in some embodiments may be used
To be carried out at 10mTorr.
In the present invention, the sputtering power of magnetron sputtering is preferably 460~600W；As that can be in some embodiments
484W.The sputtering time of the magnetron sputtering is preferably smaller than equal to 10min.In the present invention, the magnetron sputtering can be direct current
Sputtering, or radio frequency (RF) sputtering；When being sputtered using radio frequency (RF), the frequency of radio frequency is preferably 5~20MHz.The present invention
In, it is conventional sputter distance in this field that the sputtering distance of the magnetron sputtering, which is not particularly limited, such as can for 5~
15cm。
For the present invention after magnetron sputtering, deposition forms precursor CTO basement membrane on substrate.In the present invention, the precursor
The thickness of CTO basement membrane is preferably 150~500nm.The present invention is not particularly limited the type of the substrate, is normal in this field
Advise substrate.The present invention sputters under especially specific atmosphere and power condition under specific preparation condition, has faster system
Standby speed is conducive to carry out commercial scale production.
According to the present invention, after obtaining precursor CTO basement membrane, the precursor CTO basement membrane is moved back under protective atmosphere
Fire obtains cadmium stannate transparent conductive film.In the present invention, the thickness of the cadmium stannate transparent conductive film is preferably 150~500nm.
In the present invention, after obtaining precursor CTO basement membrane, it is close to annealing without carrying out CdS, it can be directly under protective atmosphere
It anneals.The temperature and time of the annealing is not particularly limited, and is this field conventional annealing temperature and time.This hair
In bright, the protective atmosphere is preferably argon atmosphere or nitrogen atmosphere.
Before the present invention is especially prepared under the coordinated of low oxygen concentration and sputtering power under aforementioned preparation condition
Body CTO basement membrane has high preparation speed, this is difficult to realize other preparation conditions；Moreover, obtained by under the foregoing conditions
Precursor CTO basement membrane in subsequent anneal, be close to annealing without complicated harsh CdS, and directly anneal under protective atmosphere
, this is also that cannot achieve under other preparation conditions, and the application enormously simplifies the preparation process of conductive film, and effectively
Preparation efficiency is improved, has broken the limitation for being only capable of laboratory preparation, can be realized industrialization large-scale production, be commercialized
Preparation and application.And the experimental results showed that, the electrical and optical performance of cadmium stannate transparent conductive film produced by the present invention is obviously excellent
In existing commercialization TCO film product.
The present invention also provides cadmium stannate transparent conductive films made from above-mentioned each technical solution.The present invention also provides one kind
Solar battery, the TCO transparent conductive film in the solar battery are cadmium stannate electrically conducting transparent described in above-mentioned technical proposal
Film.
For a further understanding of the present invention, the preferred embodiment of the invention is described below with reference to embodiment, still
It should be appreciated that these descriptions are only further explanation the features and advantages of the present invention, rather than to the claims in the present invention
Limitation.
Embodiment 1
The preparation of 1.1 precursor CTO basement membranes:
A. with SnO2- CdO is target (SnO2Molar ratio with CdO is 33:67), glass substrate is placed in magnetron sputtering chamber
Interior, the sputtering distance adjusted between target and substrate is 6.7cm；
B. sputtering chamber is vacuumized, until vacuum degree≤2.5E-6Torr；
C. gas (Ar and O are passed through into sputtering chamber2), Ar flow is 72sccm, O2Flow is 8sccm, is made in sputter chamber
Air pressure be maintained at 10mTorr, and O2The volume ratio for accounting for mixed gas is 10%；
D. radio-frequency sputtering is used, sputtering power 484W, rf frequency 13.56MHz sputter 9.5min, in glass lined
Deposition forms precursor CTO basement membrane (being denoted as 1-1#) on bottom.The results show that its deposition rate is
1.2 setting control samples:
It is carried out according to above-mentioned 1.1 preparation process, unlike, in step c, 100% O is passed through into sputtering chamber2(note
For 1-2#).The results show that its deposition rate is
It is carried out according to above-mentioned 1.1 preparation process, unlike, in step d, sputtering power is 245W (being denoted as 1-3#).
The results show that its deposition rate is
As can be seen that the formation speed of sample 1-2#, 1-3# are very slow, it is difficult to carry out industrial production, be only limitted to laboratory system
Standby research；And in the 1-1# sample of the application, deposition rate improves several times, can be realized technical grade production.
Embodiment 2
The preparation and performance test of cadmium stannate transparent conductive film:
2.1 anneal the resulting 1-2# precursor CTO basement membrane of embodiment 1 20min at 650 DEG C, and following four is respectively adopted
Annealing way: (being denoted as 2-2#a) 1. is annealed directly under Ar protective atmosphere；2. covering glass in gained precursor CTO membrane surface
Glass, Ar protective atmosphere (are denoted as 2-2#b)；3. gained precursor CTO basement membrane to be close to annealing with CdS, Ar protective atmosphere (is denoted as
2-2#c)；4. gained precursor CTO basement membrane to be close to annealing with CdSe, Ar protective atmosphere (is denoted as 2-2#d).
To the 1-2# precursor CTO basement membrane before annealing and 4 kinds of cadmium stannate electrically conducting transparent membrane samples (2-2#a, 2-2# after annealing
B, 2-2#c, 2-2#d) it carries out translucidus and can detect and detected with electric property, testing result difference is as shown in Figure 3 and Figure 4
(wherein, Fig. 3 is the saturating curve graph of light of above-mentioned 5 kinds of samples, and abscissa is wavelength, and ordinate is transmitance；Fig. 4 is above-mentioned 5 kinds of samples
The Resistivity testing figure of product, abscissa are the sample under different annealing way, and ordinate is resistivity).
As seen from Figure 3, the saturating effect difference of the light of sample 2-2#a, 2-2#b, 2-2#c, 2-2#d is larger, only sample
The translucency of 2-2#c (being close to annealing with CdS) has the saturating effect of good light compared to there is very big promotion before annealing；It that is to say
It says, for the 1-2# precursor CTO basement membrane obtained under 100% total oxygen atmosphere, needs using the annealing side for being close to annealing with CdS
Formula could obtain good optical property.As seen from Figure 4, the resistivity of 2-2#c sample is minimum, and electric conductivity is optimal.
2.2 by the resulting 1-1# precursor CTO basement membrane of embodiment 1 according to 2.1 preparation method, respectively in four kinds of annealing way
4 kinds of cadmium stannate electrically conducting transparent membrane samples: 2-1#a (directly annealing under Ar protective atmosphere), 2-1#b (precursor CTO base are made down
Film surface cover glass, Ar protective atmosphere), 2-1#c (be close to CdS annealing, Ar protective atmosphere), 2-1#d it is (tight with CdSe
Patch annealing, Ar protective atmosphere).
To before annealing 1-1# precursor CTO basement membrane and annealing after 4 kinds of samples (2-1#a, 2-1#b, 2-1#c, 2-1#d) into
Row translucidus can be detected and be detected with electric property, and (wherein, Fig. 5 is above-mentioned 5 kinds to testing result as shown in Figure 5 and Figure 6 respectively
The saturating curve graph of the light of sample, abscissa are wavelength, and ordinate is transmitance；Fig. 6 is the Resistivity testing figure of above-mentioned 5 kinds of samples,
Abscissa is the sample under different annealing way, and ordinate is resistivity).
As seen from Figure 5, compared to the sample 1-1# before annealing, the saturating effect of light of 4 kinds of samples after annealing is obvious
It is promoted, moreover, the saturating effect of the light of sample 2-1#a, 2-1#b, 2-1#c, 2-1#d is similar, difference is little；In other words, for
The 1-1# precursor CTO basement membrane obtained under 10% oxygen-containing atmosphere, can directly anneal under protective atmosphere, can reach and CdS
It is close to the comparable translucency of annealing way, it is therefore not necessary to which carrying out CdS is close to annealing, anneals directly under protective atmosphere.
As seen from Figure 6, although sample 2-1#a (directly annealing under protective atmosphere) is than sample 2-1#c's (being close to annealing with CdS)
Resistivity is slightly higher, but the resistivity of sample 2-1#a is still suitable with the commercialization resistivity of TCO, reaches the performance of commercialization TCO
Standard.
2.3 by sample 2-2#c, sample 2-1#a and commercialization SnO2The optics of film (producer provides by Pilkington), electricity
Performance comparison is referring to table 1:
The performance comparison of 1 three kinds of TCO films of table
As can be seen from Table 1, the optics of sample 2-1#a (no to be close to annealing, directly anneal under protective atmosphere), electricity
Performance is substantially better than existing commercially produced product；Although the optics of 2-1#a, electric property ratio 2-2#c (splash under 100% total oxygen atmosphere
Penetrate, annealing be close to CdS) it is slightly lower but also very close.
By above-mentioned test result it is found that the preparation method according to the application is directly being protected without carrying out CdS abutting annealing
It anneals under shield property atmosphere, enormously simplifies annealing process, can be realized industrial scale production.In addition, the application is made
Product (no be close to annealing, directly anneal under protective atmosphere) though optics, electric property is than laboratory level grade product
(sputter under 100% total oxygen atmosphere, be close to CdS annealing) is slightly lower, but has also been closer to, and importantly, the application system
Standby mode has broken the limitation of laboratory preparation, has been able to carry out industrialized production, and has than the performance of existing commercially produced product
It is obviously improved, this is for TCO film field, undoubtedly significant progress and contribution.
The above description of the embodiment is only used to help understand the method for the present invention and its core ideas.To these embodiments
A variety of modifications will be readily apparent to those skilled in the art, the general principles defined herein can be with
Without departing from the spirit or scope of the present invention, it realizes in other embodiments.Therefore, the present invention will not be limited
In the embodiments shown herein, and it is to fit to widest model consistent with the principles and novel features disclosed in this article
It encloses.
Claims (10)
1. a kind of production technology of cadmium stannate transparent conductive film, which comprises the following steps:
A) target is carried out in mixed-gas environment to magnetron sputtering, obtain precursor CTO basement membrane；
The target is by SnO2The target formed with CdO, or be Sn-Cd alloy target material；
The mixed gas is argon gas and oxygen, wherein the volume fraction that oxygen accounts for the mixed gas is 5%~15%；
B) the precursor CTO basement membrane is annealed under protective atmosphere, obtains cadmium stannate transparent conductive film.
2. production technology according to claim 1, which is characterized in that in the step a), the air pressure of the mixed gas
For 5~30mTorr.
3. production technology according to claim 1, which is characterized in that in the step a), the sputtering of the magnetron sputtering
Power is 460~600W.
4. production technology according to claim 3, which is characterized in that in the step a), the sputtering of the magnetron sputtering
Time is less than or equal to 10min.
5. production technology according to claim 1, which is characterized in that described by SnO in the step a)2It is formed with CdO
Target in, SnO2Molar ratio with CdO is 1:(1.9~2.1).
6. production technology according to claim 1, which is characterized in that in the step a), the flow of argon gas is 20~
500sccm；The flow of oxygen is 1~100sccm.
7. production technology according to claim 1, which is characterized in that in the step b), the protective atmosphere is argon
Gas atmosphere or nitrogen atmosphere.
8. production technology according to claim 1, which is characterized in that the cadmium stannate transparent conductive film with a thickness of 150
~500nm.
9. cadmium stannate transparent conductive film made from production technology according to any one of claims 1 to 8.
10. a kind of solar battery, which is characterized in that the TCO transparent conductive film in the solar battery is claim 9 institute
The cadmium stannate transparent conductive film stated.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710428907.1A CN109037391A (en) | 2017-06-08 | 2017-06-08 | A kind of cadmium stannate transparent conductive film, its production technology and solar battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710428907.1A CN109037391A (en) | 2017-06-08 | 2017-06-08 | A kind of cadmium stannate transparent conductive film, its production technology and solar battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109037391A true CN109037391A (en) | 2018-12-18 |
Family
ID=64629578
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710428907.1A Pending CN109037391A (en) | 2017-06-08 | 2017-06-08 | A kind of cadmium stannate transparent conductive film, its production technology and solar battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109037391A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111129207A (en) * | 2018-11-01 | 2020-05-08 | 杭州朗旭新材料科技有限公司 | Cadmium stannate transparent conductive film, cadmium telluride cell preparation method and thin film solar cell |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102576743A (en) * | 2009-05-18 | 2012-07-11 | 第一太阳能有限公司 | Cadmium stannate TCO structure with diffusion barrier layer and separation layer |
| CN102569504A (en) * | 2010-12-17 | 2012-07-11 | 通用电气公司 | Method for forming cadmium tin oxide layer and a photovoltaic device |
| CN105585317A (en) * | 2014-10-20 | 2016-05-18 | 北京有色金属研究总院 | Cadmium stannate target material and preparation method thereof |
| CN106367720A (en) * | 2016-09-07 | 2017-02-01 | 中国科学院电工研究所 | Cadmium stannate (CTO) film annealing method |
-
2017
- 2017-06-08 CN CN201710428907.1A patent/CN109037391A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102576743A (en) * | 2009-05-18 | 2012-07-11 | 第一太阳能有限公司 | Cadmium stannate TCO structure with diffusion barrier layer and separation layer |
| CN102569504A (en) * | 2010-12-17 | 2012-07-11 | 通用电气公司 | Method for forming cadmium tin oxide layer and a photovoltaic device |
| CN105585317A (en) * | 2014-10-20 | 2016-05-18 | 北京有色金属研究总院 | Cadmium stannate target material and preparation method thereof |
| CN106367720A (en) * | 2016-09-07 | 2017-02-01 | 中国科学院电工研究所 | Cadmium stannate (CTO) film annealing method |
Non-Patent Citations (1)
| Title |
|---|
| 董玉峰等: ""氧浓度和衬底温度对透明导电Cd2SnO4薄膜光学性质的影响"", 《重庆邮电学院学报》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111129207A (en) * | 2018-11-01 | 2020-05-08 | 杭州朗旭新材料科技有限公司 | Cadmium stannate transparent conductive film, cadmium telluride cell preparation method and thin film solar cell |
| CN111129207B (en) * | 2018-11-01 | 2022-02-08 | 杭州朗旭新材料科技有限公司 | Cadmium stannate transparent conductive film, cadmium telluride cell preparation method and thin film solar cell |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102569442B (en) | Thin film solar cell and manufacturing method thereof | |
| Perrenoud et al. | The use of aluminium doped ZnO as transparent conductive oxide for CdS/CdTe solar cells | |
| CN102779864B (en) | Cadmium telluride thin-film battery and manufacturing method thereof | |
| Li et al. | Comparison of ITO, In2O3: Zn and In2O3: H transparent conductive oxides as front electrodes for silicon heterojunction solar cell applications | |
| US20120132268A1 (en) | Electrode, photovoltaic device, and method of making | |
| AU2010286811A2 (en) | Doped transparent conductive oxide | |
| TWI558830B (en) | Method of making a transparent conductive oxide layer | |
| Liu et al. | Indium tin oxide with titanium doping for transparent conductive film application on CIGS solar cells | |
| CN104332515B (en) | Copper indium diselenide nanocrystalline silicon thin film solar cell with graphene as conductive material and preparation method thereof | |
| CN112490363B (en) | Preparation method of perovskite solar cell based on magnetron sputtering zinc oxide/tin dioxide double electron transmission layer | |
| CN105714262A (en) | Preparation method of preferred growing ITO transparent conductive film | |
| CN201402813Y (en) | Thin-film solar cell with high photon-to-electron conversion efficiency | |
| Zhou et al. | Innovative wide-spectrum Mg and Ga-codoped ZnO transparent conductive films grown via reactive plasma deposition for Si heterojunction solar cells | |
| CN107217232A (en) | A kind of method for improving zinc oxide transparent conductive film chemical stability | |
| Caudevilla et al. | Indium tin oxide obtained by high pressure sputtering for emerging selective contacts in photovoltaic cells | |
| CN101393942B (en) | Polycrystalline-silicon carbide lamination thin-film solar cell | |
| CN103081028A (en) | Multilayer transparent electroconductive film and method for manufacturing same, as well as thin-film solar cell and method for manufacturing same | |
| CN109037391A (en) | A kind of cadmium stannate transparent conductive film, its production technology and solar battery | |
| CN101882653B (en) | Preparation method of solar battery based on nano CdS (Cadmium Sulfide) film | |
| CN101705473B (en) | Physical vapor deposition equipment for use in study on light trapping structure of silicon thin-film battery | |
| CN103779430A (en) | Conductive antireflection film of crystalline silicon solar cell and crystalline silicon solar cell | |
| CN105957924A (en) | Method for preparing preferred orientation ITO photoelectric thin film by ZnO buffer layer | |
| CN116322072A (en) | Preparation method of semitransparent perovskite solar cell | |
| CN102433545A (en) | Suede-structured ZnO film prepared by alternative growth technology and application thereof | |
| CN207009459U (en) | The silicon based hetero-junction solar cell that a kind of tow sides can generate electricity |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20181218 |
|
| RJ01 | Rejection of invention patent application after publication |