CN103451599B - A kind of have photo-thermal and work in coordination with the cadmium telluride of sending a telegraph/Tellurobismuthite integration nano structural material and method for making thereof - Google Patents
A kind of have photo-thermal and work in coordination with the cadmium telluride of sending a telegraph/Tellurobismuthite integration nano structural material and method for making thereof Download PDFInfo
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- CN103451599B CN103451599B CN201310362759.XA CN201310362759A CN103451599B CN 103451599 B CN103451599 B CN 103451599B CN 201310362759 A CN201310362759 A CN 201310362759A CN 103451599 B CN103451599 B CN 103451599B
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- MARUHZGHZWCEQU-UHFFFAOYSA-N 5-phenyl-2h-tetrazole Chemical compound C1=CC=CC=C1C1=NNN=N1 MARUHZGHZWCEQU-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 239000000463 material Substances 0.000 title claims abstract description 47
- 238000000034 method Methods 0.000 title claims abstract description 24
- 230000010354 integration Effects 0.000 title claims abstract description 20
- 239000000758 substrate Substances 0.000 claims abstract description 33
- 239000011521 glass Substances 0.000 claims abstract description 20
- 229910052714 tellurium Inorganic materials 0.000 claims abstract description 15
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims abstract description 15
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 44
- 238000004544 sputter deposition Methods 0.000 claims description 35
- 229910052786 argon Inorganic materials 0.000 claims description 22
- 238000000151 deposition Methods 0.000 claims description 15
- 239000007789 gas Substances 0.000 claims description 14
- 238000002360 preparation method Methods 0.000 claims description 11
- 238000004062 sedimentation Methods 0.000 claims description 10
- 230000008021 deposition Effects 0.000 claims description 9
- 230000001105 regulatory effect Effects 0.000 claims description 9
- 238000002425 crystallisation Methods 0.000 claims description 6
- 230000008025 crystallization Effects 0.000 claims description 6
- 229910052797 bismuth Inorganic materials 0.000 claims description 4
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 4
- 238000009825 accumulation Methods 0.000 claims description 3
- 238000010849 ion bombardment Methods 0.000 claims description 3
- 238000005477 sputtering target Methods 0.000 claims description 3
- 229910004613 CdTe Inorganic materials 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 18
- 238000001228 spectrum Methods 0.000 abstract description 16
- 238000006243 chemical reaction Methods 0.000 abstract description 15
- 238000005286 illumination Methods 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 7
- 229910052724 xenon Inorganic materials 0.000 description 7
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 7
- 238000001755 magnetron sputter deposition Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 230000005676 thermoelectric effect Effects 0.000 description 6
- 230000005611 electricity Effects 0.000 description 5
- 230000001052 transient effect Effects 0.000 description 5
- 238000013461 design Methods 0.000 description 4
- 230000001965 increasing effect Effects 0.000 description 4
- 238000002329 infrared spectrum Methods 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 239000002070 nanowire Substances 0.000 description 3
- 230000003064 anti-oxidating effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000002073 nanorod Substances 0.000 description 2
- 238000002211 ultraviolet spectrum Methods 0.000 description 2
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 2
- 239000008186 active pharmaceutical agent Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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
A kind of have photo-thermal and work in coordination with the cadmium telluride of sending a telegraph/Tellurobismuthite integration nano structural material, it is on the conducting surface of conducting glass substrate, deposit one deck cadmium telluride nanometer rod layer, deposit the Tellurobismuthite layer of tellurium doping on cadmium telluride nanometer rod layer surface again, form cadmium telluride/Tellurobismuthite integration nano structural material.This material can convert the light and heat in solar spectrum to electric energy simultaneously, realizes photo-thermal and works in coordination with the effect utilizing conversion.The invention discloses its method for making.
Description
Technical field
The present invention relates to and there is photo-thermal work in coordination with cadmium telluride (CdTe)/Tellurobismuthite (Bi utilizing effect to send a telegraph
2te
3) integrated material and method for making thereof.
Background technology
Sun power as the new forms of energy of cleanliness without any pollution, current vigorously advocate the background of low-carbon economy under, carry vital task that national energy-saving reduces discharging and be subject to everybody extensive concern.Solar spectrum energy 99% all concentrates on UV-light to infrared band.Therefore, the photoelectric conversion technique of sun power mainly contains the thermo-electric conversion utilizing the photovoltaic cell of uv-vis spectra He utilize infrared heat energy.But photovoltaic cell not only cannot absorb the infrared spectra of more than 800nm in solar spectrum, and the used heat that infrared spectra produces also will cause the bulk temperature of photovoltaic cell to rise, and then causes power conversion efficiency (pce) decline about 5-15%.
On the other hand, in theory, most solar radiation can be converted to heat energy.By thermoelectric effect, the thermograde that solar thermal energy produces can be converted to electric energy, and report many Thermoelectric Generators at present, due to the restriction of himself material behavior, its efficiency of conversion is less than 5%.Therefore, in order to the full spectrum realizing solar spectrum utilizes, photovoltaic cell and Thermoelectric Generator are assembled into a system to carry out the conversion of solar spectrum by people, and solar spectrum is divided into UV spectrum and infrared spectra by a beam splitting lens.UV spectrum part is changed for the absorption of photovoltaic cell, and infrared portions is used for thermo-electric device thermo-electric conversion.But, nearly all solar photothermoelectric system is all the macroscopic view combination of discrete photovoltaic cell and thermo-electric device, and the integration of unrealized material horizontal, therefore still really cannot solve absorption and the utilization of the full spectrum of sun power, the heat effect that the infrared spectra that simultaneously cannot absorb produces also will reduce power conversion efficiency (pce).
In order to solar spectrum be carried out the conversion of full spectrum in a material, realizing photo-thermal in solar spectrum and changing simultaneously.We devise the integrated material of photoelectric material and thermoelectric material, utilize best photovoltaic material CdTe and thermoelectric material Bi
2te
3, by the integrated design of current carrier (CdTe in bottom, Bi
2te
3on top), utilize magnetron sputtering method, successfully prepare CdTe nanometer stick array and stratiform Bi
2te
3integrated material.CdTe/Bi is shown through sign
2te
3the electrical integrated material of photo-thermal can convert the light and heat in solar spectrum to electric energy simultaneously, realizes collaborative enhancing and reaches the effect that photo-thermal works in coordination with utilization conversion.
Summary of the invention
We utilize p-n junction principle, devise photothermal integrated formed material, and its substrate is conductive glass, and lower floor is the CdTe of p-type, and upper strata is the Bi of N-shaped
2te
3.CdTe and Bi
2te
3form a p-n junction.Its concrete structure as shown in Figure 1.When sunlight is from back side illuminaton, p-n junction produces photovoltaic effect, and dominant absorption Uv and visible light, the sense of current of generation as shown in Figure 1.Meanwhile, the infrared band being greater than 800nm in solar spectrum will produce heat, the Bi that the heat that in p-n junction, Carrier recombination produces also will be delivered to
2te
3bottom, so just at Bi
2te
3two ends up and down form a temperature difference, thermoelectric material Bi
2te
3this temperature difference also will be converted to electric energy simultaneously, the sense of current as shown in Figure 1.Such CdTe/Bi
2te
3integrated material is while carrying out opto-electronic conversion by solar spectrum, also also convert the heat energy produced in the heat energy in solar spectrum and p-n junction photoelectric conversion process to electric energy simultaneously, and the sense of current changed is consistent, realize collaborative enhancing, acquisition solar energy optical-thermal is collaborative utilizes effect.
Therefore, invention devises and a kind ofly has photo-thermal and work in coordination with cadmium telluride (CdTe) nanometer rod/Tellurobismuthite (Bi utilizing effect
2te
3) integrated material of laminate structure, and successfully realize design by magnetron sputtering, characterized by V-t curve and confirm the ability that integrated material works in coordination with conversion solar light and heat.
Technical scheme of the present invention is as follows:
A kind of have photo-thermal and work in coordination with the cadmium telluride of sending a telegraph/Tellurobismuthite integration nano structural material, it is on the conducting surface of conducting glass substrate, deposit one deck cadmium telluride nanometer rod layer, deposit the Tellurobismuthite layer of tellurium doping on cadmium telluride nanometer rod layer surface again, form cadmium telluride/Tellurobismuthite integration nano structural material.
Above-mentioned cadmium telluride/Tellurobismuthite integration nano structural material, described cadmium telluride nanometer rod thickness 2000-3000 nanometer.
Above-mentioned cadmium telluride/Tellurobismuthite integration nano structural material, described Tellurobismuthite thickness 300-1500 nanometer.
Above-mentioned cadmium telluride/Tellurobismuthite integration nano structural material, the volatilization of tellurium element through tellurium doping post-compensation of described Tellurobismuthite layer, atomicity ratio is bismuth: tellurium=2:2.9 ~ 2:3.15.
Above-mentioned cadmium telluride/Tellurobismuthite integration nano structural material, wire is drawn as positive pole at Tellurobismuthite layer elargol, the conducting surface of conducting glass substrate draws wire with elargol and namely forms battery as negative pole, as shown in Figure 1, namely produce voltage and current when sunlight is injected from conductive glass face.
Prepare a method for above-mentioned cadmium telluride/Tellurobismuthite integration nano structural material, it is at magnetic as shown in Figure 2
Carry out in control sputtering instrument, it comprises the steps:
The preparation of step 1. cadmium telluride nanometer rod
Cadmium telluride target to be put on the radio frequency platform 1 of the vacuum chamber 7 of magnetic control sputtering device by 1.1;
1.2 conducting glass substrates are positioned in sample table 2;
1.3 regulate the distance of sample table 2 and radio frequency platform 1 to 80-90mm, preferably 88-90mm;
1.4 pairs of vacuum chamber, thus make the vacuum tightness in vacuum chamber reach 2.0 × 10
-4pa ~ 4.0 × 10
-4pa;
1.5 conducting glass substrates are heated to 350-400 DEG C, to regulate and control the crystallization condition of cadmium telluride;
1.6 are filled with argon gas in vacuum chamber, and ar pressure is adjusted to 0.4-1.0Pa, preferably 0.4-0.5Pa, to regulate the scattering degree of cadmium telluride in the process arriving electrically-conductive backing plate sputtered out, thus regulate sedimentation rate;
1.7 apply radio-frequency voltages between the negative electrode 10 of immediately target and the anode 11 immediately after substrate (i.e. voltage of alternating current), and adjustment radio-frequency current is 81-140mA, preferably 130-140mA; Voltage is 0.37-0.60kV, preferably 0.58-0.60kV, argon gas is ionized, utilize the positive negativity generating period of AC power alternately, when sputtering target is in positive half cycle, stream of electrons is to target surface, neutralize the positive charge of its surface accumulation, and accumulate electronics, make its surface presentation negative bias, cause attracting argon ion bombardment target when the negative half-cycle of radio-frequency voltage, thus realize radio-frequency sputtering undertaken regulating by the size (i.e. alternating current and voltage of alternating current size) of radio-frequency current voltage and the CdTe that can regulate and control to sputter out number thus adjustment sedimentation rate; Deposition 1-2 hour;
The preparation of step 2. Tellurobismuthite laminate structure
Tellurobismuthite target to be put on the direct current platform 12 of the vacuum chamber 7 of magnetic control sputtering device by 2.1; Tellurium target is put into (by cadmium telluride target replacement) on the radio frequency platform 1 of magnetic control sputtering device simultaneously and carry out dual-target sputtering;
The conducting glass substrate that 2.1 steps 1 deposited cadmium telluride is positioned in sample table 2;
2.2 regulate the distance of sample table and radio frequency platform to 80-90mm, preferably 88-90mm;
2.3 pairs of vacuum chamber, thus make the vacuum tightness in vacuum chamber reach 2.0 × 10
-4pa ~ 4.0 × 10
-4pa;
2.4 conducting glass substrates are heated to 350-450 DEG C, to regulate and control the crystallization condition of Tellurobismuthite;
2.5 are filled with argon gas in vacuum chamber, and ar pressure is adjusted to 1.5-2.0Pa, preferably 1.9-2.0Pa, to regulate the scattering degree of Tellurobismuthite in the process arriving electrically-conductive backing plate sputtered out, thus regulate sedimentation rate;
2.6 regulate radio-frequency current to be 95-100mA, preferably 99-100mA; Voltage is 0.38-0.42kV, preferably 0.39-0.40kV;
2.7 regulate galvanic current to be 80-100mA, preferably 80-90mm; Voltage is 0.25-0.27kV, preferably 0.25-0.26kV;
Deposition 1-2 hour, i.e. obtained described cadmium telluride/Tellurobismuthite integration nano structural material.
Cadmium telluride (CdTe) nanometer rod/Tellurobismuthite (Bi obtained
2te
3) integrated material of laminate structure can convert the light and heat in solar spectrum to electric energy simultaneously, realize photo-thermal and work in coordination with the effect utilizing conversion.
Accompanying drawing explanation
Fig. 1 is the battery structure schematic diagram of material of the present invention and its composition.
Fig. 2 is the schematic diagram of magnetic control sputtering device (JGP-450a type multi-target magnetic control sputtering depositing system, Chinese Academy of Sciences Shenyang scientific instrument development center company limited), wherein: 1 is radio frequency platform; 2 is sample table; 3 is baffle plate; 4 is argon inlet mouth; 5 is mass flowmeter; 6 is vacuum extractor (comprising mechanical pump and molecular pump); 7 is vacuum chamber; 8 is the sample table axis of rotation; 9 is computer heating control power supply; 10 is radio frequency platform negative electrode; 11 is anode; 12 is direct current platform; 13 is direct current platform negative electrode.
Fig. 3 is the XRD figure of the product adopting the method for embodiments of the invention to obtain.
Fig. 4 is the stereoscan photograph of embodiment 1.
Fig. 5 is the stereoscan photograph partial enlarged drawing of embodiment 1.
Fig. 6 is the V-t curve obtaining the collaborative utility of product photo-thermal electricity.Its test condition is its intensity of illumination of xenon lamp is 8mW/cm
2.
Fig. 7 is the V-t curve obtaining the collaborative utility of product photo-thermal electricity.Its test condition is its intensity of illumination of xenon lamp is 25mW/cm
2.
Fig. 8 is the V-t curve obtaining the collaborative utility of product photo-thermal electricity.Its test condition is its intensity of illumination of xenon lamp is 50mW/cm
2.
Fig. 9 is the V-t curve obtaining the collaborative utility of product photo-thermal electricity.Its test condition is its intensity of illumination of halogen lamp is 8mW/cm
2.
Figure 10 is the V-t curve obtaining the collaborative utility of product photo-thermal electricity.Its test condition is its intensity of illumination of halogen lamp is 25mW/cm
2.
Figure 11 is the stereoscan photograph of embodiment 2.
Embodiment
The present invention adopts two step magnetron sputtering method preparations to have the method that photo-thermal works in coordination with the special nanostructure cadmium telluride/Tellurobismuthite integrated material utilizing effect
In the present invention, the resistance of CdTe target is comparatively large, and the magnetically controlled sputter method therefore adopted is radio-frequency sputtering.On the contrary, Bi
2te
3the resistance of target is less, and the magnetically controlled sputter method therefore adopted is d.c. sputtering, and wherein during dual-target sputtering, Te target is used for Bi
2te
3adulterate, adopt radio-frequency sputtering.
By reference to the accompanying drawings 2, the technical scheme that two step magnetron sputtering methods according to an embodiment of the invention prepare cadmium telluride (nano-wire array)/Tellurobismuthite (stratiform) is:
Cadmium telluride target (as commercial cadmium telluride target) is put on the radio frequency platform 1 of the vacuum chamber 7 of magnetic control sputtering device, conducting glass substrate is positioned in sample table 2, regulate the distance d of sample table 2 and radio frequency platform 1 to predetermined distance (d=80-90mm) within the scope of this, thus the distance making the CdTe sputtered out arrive substrate drops in suitable scope;
Open vacuum extractor 6 pairs of vacuum chambers 7 and vacuumize the anti-oxidation preparing for next step pours argon gas of deflating, make vacuum tightness in vacuum chamber 7 reach preset value (as 2.0 × 10
-4pa ~ 4.0 × 10
-4pa);
Open computer heating control power supply, and start the sample table axis of rotation 8 and make substrate carry out rotation with certain speed, to make the film of deposition comparatively even, allow electrically-conductive backing plate temperature rise to 350 DEG C-400 DEG C to regulate and control the crystallization condition of CdTe;
Argon flow amount is regulated to be 25sccm by mass flowmeter 5.
Open argon inlet mouth 4, in vacuum chamber 7, be filled with argon gas, and adjustable pressure is 0.4-1.0Pa the CdTe that sputters out can be regulated in the scattering degree arrived in substrate process thus regulate sedimentation rate;
Target and conducting glass substrate are isolated by butterfly 3
Apply radio-frequency voltage (i.e. voltage of alternating current and electric current) between the negative electrode 10 of immediately target and the anode 11 immediately after substrate, adjustment radio-frequency current is 81mA-140mA, voltage is 0.37kV-0.60kV, utilize the positive negativity generating period of AC power alternately, when sputtering target is in positive half cycle, stream of electrons is to target surface, neutralize the positive charge of its surface accumulation, and accumulate electronics, make its surface presentation negative bias, cause attracting argon ion bombardment target when the negative half-cycle of radio-frequency voltage, thus realize radio-frequency sputtering; Regulated by the size (i.e. alternating current and voltage of alternating current size) of radio frequency current/voltage, regulate and control sputter out CdTe number thus regulate sedimentation rate; (as figure) butterfly 3, to contact vacuum-chamber wall, enables the CdTe sputtered out arrive conducting glass substrate clockwise;
Deposition 1-2 hour;
Prepare complete, close radio-frequency power supply;
To be cooled to room temperature, take out cadmium telluride target
Tellurobismuthite target (as commercial Tellurobismuthite target) is put on the direct current platform 12 of the vacuum chamber 7 of magnetic control sputtering device, tellurium target (as commercial tellurium target) is put on the radio frequency platform 1 of the vacuum chamber 7 of magnetic control sputtering device simultaneously, conducting glass substrate is positioned in sample table 2, keep sample table 2 constant with the distance d of radio frequency platform 1, thus make the Bi that sputters out
2te
3the distance arriving substrate with Te drops in suitable scope;
Open vacuum extractor 6 pairs of vacuum chambers 7 and vacuumize the anti-oxidation preparing for next step pours argon gas of deflating, make vacuum tightness in vacuum chamber 7 reach preset value (as 2.0 × 10
-4pa ~ 4.0 × 10
-4pa);
Open computer heating control power supply, and start sample and make substrate carry out rotation with certain speed from turntable 8, to make the film of deposition comparatively even, allow electrically-conductive backing plate temperature rise to 350 DEG C-450 DEG C to regulate and control Bi
2te
3with the crystallization condition of Te;
Argon flow amount is regulated to be 25sccm by mass flowmeter 5.
Open argon inlet mouth 4, in vacuum chamber 7, be filled with argon gas, and adjustable pressure is 1.5-2.0Pa can regulate the Bi sputtered out
2te
3sedimentation rate is regulated in the scattering degree arrived in substrate process with Te;
Target and conducting glass substrate are isolated by butterfly 3
Apply radio-frequency voltage (i.e. voltage of alternating current and electric current) between the negative electrode 10 of immediately target and the anode 11 immediately after substrate, adjustment radio-frequency current is 95mA-100mA, voltage is 0.38kV-0.42kV, apply volts DS and electric current between the negative electrode 13 of immediately target and the anode 11 immediately after substrate simultaneously, adjustment galvanic current is 80mA-100mA, voltage is 0.25kV-0.27kV, is regulated by the size of radio frequency current/voltage and galvanic current/voltage, the Bi regulating and controlling to sputter out
2te
3with Te number thus regulate sedimentation rate; (as figure) butterfly 3, to contact vacuum-chamber wall, makes the Bi sputtered out clockwise
2te
3cdTe nano-wire array surface can be arrived with Te;
Deposition 1-2 hour;
Prepare complete, close radio frequency and direct supply;
In the preparation process in accordance with the present invention, first to regulate the size of the distance d of sample table 2 and radio frequency platform (sputtering source) 1, sputtering pressure, substrate temperature, radio-frequency power supply, then start sputtering and can control to obtain the Cadmium telluride nanowire array be deposited on conducting glass substrate, the cadmium telluride nanometer stick array structure making magnetron sputtering deposition obtained is homogeneous, effectively ensure that being uniformly distributed of nanophase.In like manner, the preparation of stratiform Tellurobismuthite structure is applicable to.
According to the result of the experiment that the present inventor carries out, during preparation CdTe nanometer rod, sample table 2 is about 88-90mm with the preferred distance of radio frequency platform 1, preferred sputtering operating air pressure is about 0.4-0.5Pa, preferred radio-frequency sputtering electric current is about 130-140mA, preferred sputtering voltage is about 0.58-0.60kV, and preferred substrate temperature is in about 350-400 DEG C scope; Under these preferred parameters, the nanorod structure obtained is more homogeneous, and effect is better.Preparation laminate structure Bi
2te
3during nanometer rod, sample table 2 is about 88-90mm with the preferred distance of radio frequency platform 1, preferred sputtering operating air pressure is about 1.9-2.0Pa, preferred d.c. sputtering electric current is about 80-90mA, preferred d.c. sputtering voltage is about 0.25-0.26kV, preferred radio-frequency sputtering electric current is about 99-100mA, and preferred radio-frequency sputtering voltage is about 0.39-0.40kV, and preferred substrate temperature is in about 350-450 DEG C scope; Under these preferred parameters, the Bi obtained
2te
3laminate structure effect is better.
Embodiment 1:
(1) preparation of cadmium telluride/Tellurobismuthite integration nano structural material
Regulate the distance d=90mm of sample table 2 and radio frequency platform 1
Vacuum chamber 7 is vacuumized, makes vacuum tightness in vacuum chamber 7 reach 3.4 × 10
-4pa;
Open computer heating control power supply 9, and open sample from turntable 8, allow base reservoir temperature rise to 350 DEG C;
Be filled with argon gas toward vacuum chamber 7, and adjustable pressure is 0.4Pa;
Adjustment radio-frequency current is 140mA, and voltage is 0.60kV
Depositing time 2h;
Prepare complete, close radio-frequency power supply, naturally cool to room temperature 25 DEG C, take out target;
By Bi
2te
3target is positioned on direct current platform, is positioned on radio frequency platform simultaneously, vacuumizes Te target vacuum chamber 7, makes vacuum tightness in vacuum chamber 7 reach 3.4 × 10
-4pa;
Open computer heating control power supply 9, and open sample from turntable 8, allow base reservoir temperature rise to 350 DEG C;
Be filled with argon gas toward vacuum chamber 7, and adjustable pressure is 2.0Pa;
Adjustment galvanic current is 80mA, and voltage is 0.25kV;
Adjustment radio-frequency current is 100mA, and voltage is 0.40kV;
Depositing time 1h;
Prepare complete, close radio-frequency power supply, naturally cool to room temperature 25 DEG C;
(2) sample characterization
Adopt X-ray diffractometer to carry out material phase analysis to obtained cadmium telluride/Tellurobismuthite integrated material, as shown in Figure 3, illustrate that obtained material (00l) direction directional property is strong.The integrated material that above-mentioned magnetron sputtering method is obtained is observed under a scanning electron microscope, success obtains the appearance structure of cadmium telluride nanorod structure and Tellurobismuthite laminate structure integrated material, stereoscan photograph as shown in Figures 4 and 5, show cadmium telluride nanometer rod thickness 2000 nanometer, Tellurobismuthite thickness 300 nanometer.
Analyze Tellurobismuthite laminate structure with energy spectrometer, result shows bismuth: tellurium=2:2.96.
Carry out V-t curve sign to integrated material, testing method as shown in Figure 1.First the xenon lamp adopting thermal value few is 8mW/cm at power
2irradiate, as shown in Figure 6, when rayed, transient voltage increases rapidly the graph of a relation of time and voltage, and it is p-n junction photovoltaic effect, after along with the increase of light application time, voltage is comparatively steady, and when low light intensity is described, heat is less, and thermoelectric effect is not obvious.When increasing xenon lamp power is to 25mW/cm
2time, as shown in Figure 7, transient voltage value comparatively 8mW/cm
2shi Shangsheng, light application time increases voltage and steadily declines, and is obvious photovoltaic property, illustrates that heat is less, and the thermoelectric effect still less balance photovoltaic effect that is not enough to declines with the rising of heat.When xenon lamp power is increased to 50mW/cm
2time, as shown in Figure 8, moment illumination magnitude of voltage promote further, along with the growth of time, voltage continues to raise, and thermoelectric effect starts to manifest and realizes the effect that photo-thermal works in coordination with utilization.
In order to further confirmatory experiment result, the halogen lamp that we have employed heat large irradiates, when intensity of illumination is 8mW/cm
2time, as shown in Figure 9, when rayed, transient voltage increases to rapidly a definite value to the graph of a relation of time and voltage, and due under same intensity of illumination, the minimizing of different ultraviolet-visible spectrum wave band, its photovoltaic effect weakens, and therefore its transient voltage value is little compared with xenon lamp.Along with the increase of light application time, voltage is also along with slowly increasing to certain value, and its result shows, thermoelectric effect is obvious, achieves the effect that photo-thermal works in coordination with utilization.When intensity of illumination is increased to 25mW/cm
2time, as shown in Figure 10, transient voltage value comparatively 8mW/cm
2in time, significantly increases, and thermoelectric effect continues to strengthen, and has more manifested that photo-thermal is collaborative utilizes effect.
Embodiment 2:
(1) preparation of cadmium telluride/Tellurobismuthite integration nano structural material
Regulate the distance d=90mm of sample table 2 and radio frequency platform 1
Vacuum chamber 7 is vacuumized, makes vacuum tightness in vacuum chamber 7 reach 3.4 × 10
-4pa;
Open computer heating control power supply 9, and open sample from turntable 8, allow base reservoir temperature rise to 400 DEG C;
Pour argon gas toward vacuum chamber 7, and adjustable pressure is 0.4Pa;
Adjustment radio-frequency current is 130mA, and voltage is 0.60kV
Depositing time 1.5h;
Prepare complete, close radio-frequency power supply, naturally cool to room temperature 25 DEG C, take out target;
By Bi
2te
3target is positioned on direct current platform, is positioned on radio frequency platform simultaneously, vacuumizes Te target vacuum chamber 7, makes vacuum tightness in vacuum chamber 7 reach 3.4 × 10
-4pa;
Open computer heating control power supply 9, and open sample from turntable 8, allow base reservoir temperature rise to 450 DEG C;
Pour argon gas toward vacuum chamber 7, and adjustable pressure is 2.0Pa;
Adjustment galvanic current is 80mA, and voltage is 0.25kV;
Adjustment radio-frequency current is 100mA, and voltage is 0.40kV;
Depositing time 1.5h;
Prepare complete, close radio-frequency power supply, naturally cool to room temperature 25 DEG C;
Change CdTe and Bi
2te
3depositing time thus change thickness proportion, the scanning electron microscope (SEM) photograph of the product of acquisition as shown in figure 11, shows cadmium telluride nanometer rod thickness 2200 nanometer, Tellurobismuthite thickness 1300 nanometer.
Analyze Tellurobismuthite laminate structure with energy spectrometer, result shows bismuth: tellurium=2:3.1.
At sputtering Bi
2te
3process in be equivalent to there is an annealing process to CdTe, and Bi
2te
3sputtering time increases, and therefore CdTe nanometer stick array structure has agglomeration.And Bi
2te
3there is CdTe layer below, therefore base reservoir temperature and Bi
2te
3growth temperature have a thermograde, therefore at relatively high temperatures, Bi
2te
3can stratiform be kept, and some change of CdTe nanometer stick array structure.But its product still has light-heat integration performance, meet integrated material principle design.
From above-described embodiment, we can find out the structure with the best of embodiment 1, and XRD illustrates that its directional property is also fine, and embodiment 1 adopts optimized parameter scope deposit film, therefore obtains best effect.Meanwhile, the not microstructure change of tube material or thickness proportion change, as long as and the principle that designs of integrated material consistent, just can obtain the ability that light and heat works in coordination with conversion.
Claims (2)
1. one kind has photo-thermal and works in coordination with the cadmium telluride of sending a telegraph/Tellurobismuthite integration nano structural material, it is characterized in that: it is on the conducting surface of conducting glass substrate, deposit one deck cadmium telluride nanometer rod layer, the Tellurobismuthite layer of tellurium doping is deposited again on cadmium telluride nanometer rod layer surface, form cadmium telluride/Tellurobismuthite integration nano structural material, described cadmium telluride nanometer rod thickness 2000-3000 nanometer; Described Tellurobismuthite thickness 300-1500 nanometer; Described Tellurobismuthite layer is through the volatilization of tellurium element of tellurium doping post-compensation, and atomicity ratio is bismuth: tellurium=2:2.9 ~ 2:3.15.
2. prepare a method for cadmium telluride according to claim 1/Tellurobismuthite integration nano structural material, it carries out in magnetic control sputtering device, it is characterized in that it comprises the steps:
The preparation of step 1. cadmium telluride nanometer rod layer
Cadmium telluride target to be put on the radio frequency platform (1) of the vacuum chamber (7) of magnetic control sputtering device by 1.1;
1.2 conducting glass substrates are positioned in sample table (2);
1.3 regulate the distance of sample table (2) and radio frequency platform (1) to 80-90mm;
1.4 pairs of vacuum chamber, thus make the vacuum tightness in vacuum chamber reach 2.0 × 10
-4pa ~ 4.0 × 10
-4pa;
1.5 conducting glass substrates are heated to 350-400 DEG C, to regulate and control the crystallization condition of cadmium telluride;
1.6 are filled with argon gas in vacuum chamber, and ar pressure is adjusted to 0.4-1.0Pa, to regulate the scattering degree of cadmium telluride in the process arriving electrically-conductive backing plate sputtered out, thus regulate sedimentation rate;
1.7 apply between negative electrode (10) that radio frequency alternating current are pressed on immediately target and anode (11) immediately after substrate, and adjustment radio-frequency current is 81-140mA; Voltage is 0.37-0.60kV, argon gas is ionized, utilize the positive negativity generating period of AC power alternately, when sputtering target is in positive half cycle, stream of electrons, to target surface, neutralizes the positive charge of its surface accumulation, and accumulate electronics, make its surface presentation negative bias, cause attracting argon ion bombardment target when the negative half-cycle of radio-frequency voltage, thus realize radio-frequency sputtering by the size of radio frequency alternating current and voltage of alternating current carry out the CdTe regulating to regulate and control to sputter out number thus regulate sedimentation rate; Deposition 1-2 hour;
The preparation of step 2. Tellurobismuthite laminate structure
Tellurobismuthite target to be put on the direct current platform (12) of the vacuum chamber (7) of magnetic control sputtering device by 2.1; The radio frequency platform (1) simultaneously tellurium target being put into magnetic control sputtering device carries out dual-target sputtering;
The conducting glass substrate that 2.2 steps 1 deposited cadmium telluride is positioned in sample table (2);
2.3 regulate the distance of sample table and radio frequency platform to 80-90mm;
2.4 pairs of vacuum chamber, thus make the vacuum tightness in vacuum chamber reach 2.0 × 10
-4pa ~ 4.0 × 10
-4pa;
2.5 conducting glass substrates are heated to 350-450 DEG C, to regulate and control the crystallization condition of Tellurobismuthite;
2.6 are filled with argon gas in vacuum chamber, and ar pressure is adjusted to 1.5-2.0Pa, to regulate the scattering degree of Tellurobismuthite in the process arriving electrically-conductive backing plate sputtered out, thus regulate sedimentation rate;
2.7 regulate radio-frequency current to be 95-100mA; Voltage is 0.38-0.42kV;
2.8 regulate galvanic current to be 80-100mA; Voltage is 0.25-0.27kV; Deposition 1-2 hour, i.e. obtained described cadmium telluride/Tellurobismuthite integration nano structural material.
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| CN106498354B (en) * | 2016-09-18 | 2018-09-25 | 中国科学院电工研究所 | A method of preparing hexagonal Spiral morphology bismuth telluride thermal electric film |
| CN108486530A (en) * | 2018-03-16 | 2018-09-04 | 成都理工大学 | The method that on-line heating realizes the transformation of glass Be2Ti3 film p-n junctions |
| CN109950138B (en) * | 2019-04-11 | 2020-11-13 | 广东工业大学 | Nano-pillar array heterojunction and preparation method thereof |
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