CN104810249B - The method of CdS film or CdS nanostructureds is grown in CdTe thin film - Google Patents
The method of CdS film or CdS nanostructureds is grown in CdTe thin film Download PDFInfo
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- CN104810249B CN104810249B CN201510171018.2A CN201510171018A CN104810249B CN 104810249 B CN104810249 B CN 104810249B CN 201510171018 A CN201510171018 A CN 201510171018A CN 104810249 B CN104810249 B CN 104810249B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
Abstract
The present invention relates to a kind of method that CdS film or CdS nanostructureds are grown in CdTe thin film, comprise the following steps：1）CdTe thin film is fitted into quartz ampoule, is put into sintering furnace, then excludes the excessive gas in quartz ampoule；（2）Then the mixed gas of H 2 S-containing gas is passed through, heating sintering furnace is annealed to CdTe thin film；（3）Cool after annealing, take out film, obtain finished product.The present invention is put into CdTe thin film in sintering furnace, and is passed through hydrogen sulfide gas, then raises the temperature of sintering furnace, finally generates CdS film or CdS nanostructureds in CdTe thin film surface in situ.Using the advantages that this preparation method equipment is simple, cost is low, and temperature is low, without using catalyst, template in growth course.It is a kind of new method for preparing hetero-junctions, can be applicable to heterojunction structure photovoltaic solar battery（Such as CIGS, CZTS and CdTe）Preparation in.
Description
Technical field
The present invention relates to technical field of solar batteries, and in particular to CdS film or CdS nanometers are grown in CdTe thin film
The method of structure.
Background technology
At present, the traditional energy such as coal, oil occupies leading position in our life, but it is dirty with high energy consumption, height
Dye affects our daily life, and it is greatly unfavorable to be brought to our life.And the one kind of solar energy as new energy,
Because its is inexhaustible, nexhaustible, it is widely distributed the advantages that enjoy national governments to pay attention to.
CdTe base photovoltaic solar cells are one kind in second generation new energy thin film solar cell.Its core composition portion
Divide what is be made up of the CdTe absorbed layers of p-type and the CdS Window layers of n-type.Absorbed layer CdTe material is the half of a kind of direct band gap
Conductor, band gap are 1.48 eV, and this is well matched with solar spectrum.Its absorption coefficient is very high, and up to 105 cm-1, it is only necessary to
1 um cans sponge more than 99% visible ray.And the amount needed during preparing film is few, and cost is low.CdS film
It is corresponding Window layer.
It is after first growing CdS film with immersion method on ito glass, then thereon near space liter that major part, which prepares device,
Magnificent method grows CdTe thin film, then grows electrode.In the preparation process of device, an important factor be want CdTe thin film and
Pn-junction is mutually diffuseed to form between CdS film, such preparation method can form mutation in band structure, and CdS and CdTe are thin
The problem of lattice mismatch between film be present.
According to the applicant understood, CdS layer is grown in CdTe thin film surface in situ at present（Film or nanostructured）Form pn
The method of knot is not reported also.
The content of the invention
The purpose of the present invention is the method for growth in situ n-type CdS film or CdS nanostructureds in p-type CdTe thin film,
Be formed in situ pn-junction, and the pn-junction being formed in situ can take be a gradual change process, solve between CdS and CdTe thin film
The influence of existing lattice mismatch.
The concrete technical scheme of the present invention is as follows：
The method of CdS film or CdS nanostructureds is grown in a kind of CdTe thin film, is comprised the following steps：
（1）CdTe thin film is fitted into quartz ampoule, is put into sintering furnace, then excludes the excessive gas in quartz ampoule；
（2）Then the mixed gas of H 2 S-containing gas is passed through, heating sintering furnace is annealed to CdTe thin film, annealing temperature
Spend for 200 ~ 600 DEG C, annealing time is 10min ~ 3h；
（3）Cool after annealing, take out film, obtain finished product.
Step（1）In, the CdTe thin film includes substrate and film, and the thickness of film is the um of 50 nm ~ 10.
Step（1）In, the CdTe thin film includes substrate and film, and the thickness of film is 50 ~ 500nm；Above-mentioned thickness
Film is completely reformed into CdS film under annealing conditions of the present invention；And this thickness can be as the window of battery
Layer.Step（1）In, it is passed through protective gas or the excessive gas excluded in quartz ampoule is vacuumized to quartz ampoule.
The protective gas is nitrogen or argon gas.
Step（2）In, the volume of hydrogen sulfide gas accounts for mixed gas cumulative volume 0.5% ~ 100% in the mixed gas；It is logical
The size of control hydrogen sulfide gas volumetric concentration is crossed, can indirectly control play of the CdTe thin film at high temperature with hydrogen sulfide reaction
Strong degree.
Step（2）In, the air-flow of the mixed gas is 5 ~ 100 sccm；When being full of hydrogen sulfide gas in sintering furnace,
Hydrogen sulfide gas can be no longer passed through to be annealed.Following reaction occurs in above-mentioned annealing process：CdTe（s）+H2S（g）=CdS
（s）+Te2（g）+H2（g）, wherein behalf solid-state, g are gaseous state.Mixed gas air-flow selection above range main function be
The concentration of hydrogen sulfide gas is maintained, so that the progress that reaction can continue；In addition in air-flow under drive, Te2Steam is in pipe
The low-temperature zone deposition of formula sintering furnace.
Annealing temperature of the present invention is at 200 DEG C ~ 400 DEG C, or CdS film layer is formed in CdTe thin film；Annealing
When temperature is 400 ~ 600 DEG C, the CdS film layer formed in CdTe thin film has the generation of CdS nanometers；And the nanometer generated is close
Degree is first to increase to reduce afterwards.If increasing annealing time, CdTe thin film is all changed into CdS film.The present invention passes through control condition
Annealing forms CdS film, is expected to apply on CdTe base photovoltaic solar batteries, can greatly simplify the preparation flow of battery.This
The advantages of sample is equipment is simple, and cost is low etc..And absorption of the glass to light and anti-can be reduced in photovoltaic solar battery
Penetrate, direct irradiation of sunlight increases the utilization rate of light in CdS layer.
CdTe thin film of the present invention is prepared using existing method, including close spaced sublimation method, immersion method,
Vacuum vapor deposition method, magnetron sputtering method etc..The substrate of CdTe thin film can be glass substrate, sheet metal, flexible substrate, with electricity
The substrate of pole, photovoltaic cell substrate etc..
The present invention is put into CdTe thin film in sintering furnace, and is passed through hydrogen sulfide gas, then raises the temperature of sintering furnace,
Finally CdS or CdS nanostructureds are generated in CdTe thin film surface in situ.It is basis to generate CdS film or CdS nanostructureds
The annealing temperature of setting and determine, it is CdS film that annealing temperature is generated in-situ at 200 DEG C ~ 400 DEG C, and annealing temperature
What is generated at 400 ~ 600 DEG C is CdS film and CdS nanostructureds；And generate the substrate of CdS film or CdS nanometers all
For CdTe thin film.CdS layer is formed in situ in CdTe thin film（Film or nanostructured）, it is formed in situ pn-junction and solves CdS
Existing lattice mismatch etc. influences between CdTe thin film.The advantages of this method is that equipment is simple, and growth temperature is low, controllable journey
Degree is high, and suitable for the preparation of large area, feasibility circuit is provided for industrial production.
Brief description of the drawings
Fig. 1 is the SEM patterns of CdTe thin film prepared by present invention close spaced sublimation method；
Fig. 2 is the XRD spectrum of CdTe thin film prepared by present invention close spaced sublimation method；
Fig. 3 is the SEM patterns of the finished product obtained in embodiment 1；
Fig. 4 is the XRD spectrum of the finished product obtained in embodiment 1；
Fig. 5 is the SEM patterns of the finished product obtained in embodiment 2；
Fig. 6 is the XRD spectrum of the finished product obtained in embodiment 2；
Fig. 7 is the SEM Cross Section Morphology figures of the finished product obtained in embodiment 2；
Fig. 8 is the XRD spectrum of the finished product obtained in embodiment 3；
Fig. 9 is the XRD spectrum of the finished product obtained in embodiment 4；
Figure 10 is the SEM patterns that present invention high vacuum evaporation method prepares CdTe thin film；
Figure 11 is the XRD spectrum that present invention high vacuum evaporation method prepares CdTe thin film；
Figure 12 is the SEM patterns of the finished product obtained in embodiment 5；
Figure 13 is the XRD spectrum of the finished product obtained in embodiment 5.
Embodiment
In the present invention, the substrate of selection is glass substrate, and the size of substrate is 1cm*1cm.The preparation of CdTe thin film
Method is prepared using close spaced sublimation method.In X-ray diffraction（XRD）Collection of illustrative plates（*）Corresponding diffraction maximum is the CdS of hexagonal phase,
And（¨）It is corresponding, it is the CdTe of Emission in Cubic.
Close spaced sublimation method prepares CdTe thin film
Glass substrate after acetone, ethanol, deionized water are cleaned by ultrasonic min, is put into the heavy of close spaced sublimation method successively
Product room.Then vacuumize, when vacuum reaches 0.5Pa, be passed through argon gas, the speed of bleeding regulating arrives settling chamber's air pressure
2kPa.Heating source and substrate temperature are 620 DEG C and 550 DEG C.After reaching design temperature, 5min is deposited, then Temperature fall, most
After take out CdTe thin film, the thickness of film is 6.7um ± 0.3um.The CdTe thin film prepared is as growth CdS film or receives
Substrate in rice structure, is separately employed in embodiment 1, embodiment 2, embodiment 3 and embodiment 4.And test, join as a comparison
See Fig. 1 and Fig. 2, observe the SEM patterns and XRD spectrum of CdTe thin film；Fig. 1 is the CdTe thin film prepared with close spaced sublimation method
SEM patterns, from pattern, it may be seen that the granular size of CdTe thin film is smooth in micron order, particle surface.Fig. 2 is pair
The XRD spectrum answered, it can be seen that all diffraction maximums are all consistent with the CdTe structures of cubic zinc blende.
Embodiment 1
The above-mentioned CdTe thin film prepared is fitted into quartz ampoule, is put into sintering furnace, and seals, and then passes to 100sccm
Nitrogen rinse the min of quartz ampoule 5, to exclude the air in quartz ampoule；Then pass to the mixed gas of nitrogen and hydrogen sulfide（Sulphur
The volume for changing hydrogen accounts for the 5% of mixed gas cumulative volume）；The flow velocity for controlling mixed gas is 12 sccm；Sintering furnace is with 10 DEG C/min
350 DEG C are heated to, starts Temperature fall after being incubated 60min, temperature takes out film after dropping to room temperature, obtains finished product.Compare
Compared with Fig. 1, the SEM in Fig. 3 can see, by one layer of film being made up of little particle in CdTe thin film.It is true through XRD spectrum (Fig. 4)
Recognize, this layer film is CdS film；, and film is made up of two kinds of compositions, in figure（*）Corresponding diffraction maximum is hexagonal phase
CdS（These diffraction maximums come from the CdS film of generation）, and（¨）It is corresponding, it is the CdTe of Emission in Cubic（These diffraction maximums
Come from CdTe substrates）.
Embodiment 2
The above-mentioned CdTe thin film prepared is fitted into quartz ampoule, is put into sintering furnace, and seals, and then passes to 100sccm
Nitrogen rinse quartz ampoule 5min, to exclude the air in quartz ampoule；Then pass to the mixed gas of nitrogen and hydrogen sulfide（Vulcanization
The volume of hydrogen accounts for the 5% of mixed gas cumulative volume）；The flow velocity for controlling mixed gas is 10 sccm；Sintering furnace is added with 10 DEG C/min
Heat starts Temperature fall to 460 DEG C after being incubated 60min.Temperature takes out film after dropping to room temperature, obtains finished product.As shown in figure 5,
Found by sem analysis, one layer of CdS nanostructured has been formed in situ in CdTe thin film.At high temperature, CdTe and CdS reactions
Acutely, more CdS are formed, XRD（Fig. 6）Analysis confirms, is remarkably reinforced corresponding to the intensity of CdS diffraction maximum（Compare
For 350 DEG C of annealing are lower）.Fig. 7 is the sectional view of corresponding SEM patterns, from pattern as can be seen that after high annealing
CdTe thin film forms three parts, CdTe/CdS/CdS nanostructureds.
Embodiment 3
The above-mentioned CdTe thin film prepared is fitted into quartz ampoule, is put into sintering furnace, and seals, and with vavuum pump to quartz
Pipe vacuumizes, and after air pressure is reduced to 1Pa, stops pumping, and after being passed through hydrogen sulfide gas to quartz ampoule, sealing；Sintering furnace
420 DEG C are heated to 10 DEG C/min, starts Temperature fall after being incubated 60min.Temperature takes out film after dropping to room temperature, obtains into
Product.As shown in Fig. 8 XRD spectrum, also there is CdS phase structure after as can be seen from the figure being annealed in static hydrogen sulfide gas
Generation.
Embodiment 4
The above-mentioned CdTe thin film prepared is fitted into quartz ampoule, is put into sintering furnace, and seals, and then passes to 100sccm
Nitrogen rinse the min of quartz ampoule 5, to exclude the air in quartz ampoule；Then pass to the mixed gas of nitrogen and hydrogen sulfide（Sulphur
The volume for changing hydrogen accounts for the 10% of mixed gas cumulative volume）；The flow velocity for controlling mixed gas is 12 sccm；Sintering furnace is with 10 DEG C/min
560 DEG C are heated to, starts Temperature fall after being incubated 60min, temperature takes out film after dropping to room temperature, obtains finished product.From XRD
Collection of illustrative plates（Fig. 9）In it was determined that the only presence of CdS phases, is not observed any diffraction phase on CdTe thin film.This explanation
CdTe is all changed into CdS.
High vacuum evaporation method prepares CdTe thin film
Glass substrate after acetone, ethanol, deionized water are cleaned by ultrasonic 10 minutes, is put into high vacuum evaporation method successively
Settling chamber；Then vacuumize, when vacuum reaches 1 × 10-5During Pa, heating source and substrate temperature are respectively 450 DEG C and 200
℃；After reaching design temperature, 2h is deposited, then Temperature fall, finally takes out CdTe thin film, the thickness of CdTe thin film is 320nm
±6nm.The CdTe thin film prepared is used in example 5.Figure 10 is the SEM patterns of generation CdTe thin film, from pattern, Wo Menke
To see the granular size of CdTe thin film in the range of 20 ~ 40nm.Figure 11 is corresponding XRD spectrum, and all diffraction maximums all belong to
In CdTe phases.
Embodiment 5
The above-mentioned CdTe thin film prepared with high vacuum evaporation method is fitted into quartz ampoule, is put into sintering furnace, and seals, so
The nitrogen for being passed through 100sccm afterwards rinses the min of quartz ampoule 5, to exclude the air in quartz ampoule；Then pass to nitrogen and hydrogen sulfide
Mixed gas（The volume of hydrogen sulfide accounts for the 5% of mixed gas cumulative volume）；The flow velocity for controlling mixed gas is 12 sccm；Sintering
Stove is heated to 450 DEG C with 10 DEG C/min, starts Temperature fall after being incubated 120min, temperature is taken out film after dropping to room temperature, obtained
Finished product.SEM in Figure 12 be can see, and particle is significantly grown up；It was determined that the diffraction maximum of film from Figure 13 XRD spectrums
Corresponding to CdS phases, without mutually existing for CdTe；CdTe thin film is all changed into CdS film.
The invention is not restricted to above-mentioned embodiment, any use and the same or analogous preparation method of this structure, at this
The protection domain of invention is to interior.
Claims (6)
1. the method for CdS film or CdS nanostructureds is grown in a kind of CdTe thin film, it is characterised in that comprise the following steps：
(1) CdTe thin film is fitted into quartz ampoule, is put into sintering furnace, then exclude the excessive gas in quartz ampoule；
(2) mixed gas of H 2 S-containing gas is then passed through, heating sintering furnace is annealed to CdTe thin film, and annealing temperature is
200~600 DEG C, annealing time is 10min~3h；When annealing temperature is 200 DEG C~400 DEG C, it is thin that CdS is formed in CdTe thin film
Film layer；When annealing temperature is 400~600 DEG C, the CdS film layer formed in CdTe thin film has the generation of CdS nanometers；
(3) cool after annealing, take out film, obtain finished product；
In step (1), the CdTe thin film includes substrate and film, and the thickness of film is 50nm~10um.
2. according to the method for claim 1, it is characterised in that in step (1), the CdTe thin film includes substrate and film,
The thickness of film is 50~500nm.
3. according to the method for claim 1, it is characterised in that in step (1), be passed through protective gas or quartz ampoule is taken out
Vacuum excludes the excessive gas in quartz ampoule.
4. according to the method for claim 3, it is characterised in that the protective gas is nitrogen or argon gas.
5. according to the method for claim 1, it is characterised in that in step (2), hydrogen sulfide gas in the mixed gas
Volume accounts for mixed gas cumulative volume 0.5%~100%.
6. according to the method for claim 1, it is characterised in that in step (2), the air-flow of the mixed gas for 5~
100sccm。
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