CN103117322A - Photovoltaic device based on polar/nonpolar heterojunctions and production method thereof - Google Patents
Photovoltaic device based on polar/nonpolar heterojunctions and production method thereof Download PDFInfo
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- CN103117322A CN103117322A CN2013100399430A CN201310039943A CN103117322A CN 103117322 A CN103117322 A CN 103117322A CN 2013100399430 A CN2013100399430 A CN 2013100399430A CN 201310039943 A CN201310039943 A CN 201310039943A CN 103117322 A CN103117322 A CN 103117322A
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Abstract
The invention discloses a photovoltaic device based on polar/nonpolar heterojunctions and a production method thereof. The photovoltaic device comprises a nonpolar layer and a polar layer. The nonpolar layer is a substrate made of a nonpolar material. The polar layer is a polar material film deposited on the nonpolar layer. The invention further discloses the production method of the photovoltaic device based on the polar/nonpolar heterojunctions. The photovoltaic device based on the polar/nonpolar heterojunctions is simple in structure and easy to produce. Remarkable photovoltaic effect can be realized by only depositing the polar material of a few cell layers on the nonpolar substrate.
Description
Technical field
The invention belongs to the photoelectric device technical field, particularly a class has heterojunction device of photovoltaic effect and preparation method thereof, specifically, is a class based on photovoltaic device of polar layer/nonpolar layer heterostructure and preparation method thereof.
Background technology
Photovoltaic effect because of its widely using value caused people's height research enthusiasm, it is having great effect and prospect aspect photocell, optical diode and light-detecting device.In traditional photovoltaic device, the built-in electric field substantially all derives from the depletion layer of semiconductor p-n junction, size [sees also document Green in micron level, M.A. Solar Cells:Operating Principles, Technology, and System Applications (Prentice Hall, Englewood Cliffs, 1982)].Along with the highly integrated and densification of present device, people need to seek more small material and realize photovoltaic effect, and conventional p-n junction photovoltaic device has seemed unsatisfactory.If can probe into the method for making less photovoltaic material, can bring the huge advance made of numerous applications undoubtedly, more existing nano photovoltaic devices arise at the historic moment and [see also document Tian, B.et al.Coaxial silicon nanowires as solar cells and nanoelectronic power sources.Nature449 in the world at present, 885-889 (2007) and Tang, J., Huo, Z., Brittman, S., Gao, H.﹠amp; Yang, P. Solution-processed core-shell nanowires for efficient photovoltaic ceels.Nat.Nanotechnol.6,568-572 (2011)].Problem on size, the photovoltaic structure of main flow is take p-n junction as the basis now, and most of material the built-in electric field of producing is very not strong, and photovoltaic effect is outstanding not to the utmost.
Recent research shows, the transition metal oxide heterojunction is strong and continuous interaction because of it, can show some very peculiar effects at nanoscale, the controlled oxide heterogeneous structure material that particularly polarizes provides a kind of new thinking for the photovoltaic device of making nanoscale.The inventor finds that in polar layer/nonpolar layer heterostructure at several structure cell yardsticks, polar material can provide internal electric field, and this electric field is strong and stable.When there was illumination in the external world, this material produced photo-generated carrier to photonic absorption, and they are separated under the internal electric field effect of polar material: move to the low direction of electromotive force in the hole, and electronics moves to the high direction of electromotive force.Can collect these charge carriers at surface and interface of materials making surface electrode and hearth electrode, thus the photovoltaic effect of observing.
Polar layer/nonpolar layer heterostructure device structure and preparation are simple, and size can be accomplished only several nanosizeds, and its photovoltaic effect also is easy to get, and has the prospect that attracts people's attention.And in this structure, the combination of some polarity and non-polar material, can cause because polarity is discontinuous electronics reconstruct, can produce at the interface two-dimensional electron gas can be as natural hearth electrode; Or some non-polar material self can conduct electricity, and observes photovoltaic effect for making easily hearth electrode.
Summary of the invention
In view of this, the invention provides a class based on photovoltaic device of polar/non-polar heterojunction and preparation method thereof.This device deposits the polar material film thereon take non-polar material as substrate, can demonstrate obvious photovoltaic effect.
According to an aspect of the present invention, propose a kind of photovoltaic device based on the polar/non-polar heterojunction, this photovoltaic device comprises nonpolar layer and polar layer, wherein:
Described nonpolar layer is for using the substrate of non-polar material;
Described polar layer is the polar material film that is deposited on described nonpolar layer.
According to a further aspect in the invention, propose a kind of preparation method of the photovoltaic device based on the polar/non-polar heterojunction, the method comprises the following steps:
Step 2, the substrate of strontium titanate after cleaning with the corrosion of hydrofluoric acid cushioning liquid be after a period of time, obtains the substrate of strontium titanate of the crystal plane direction 001 that the monohapto of titanyl layer stop; In an atmospheric oxygen atmosphere, the substrate of strontium titanate that the titanyl layer monohapto after etching stopped is heated to 900～1000 ℃ of annealing afterwards, and annealing time is 2 hours;
Step 3, the vacuum coating of the substrate of strontium titanate after lanthanum aluminate target and processing being put into pulsed laser deposition equipment is indoor, after being evacuated to high vacuum state with mechanical pump and the molecular pump back end vacuum that vacuum coating is indoor, passing into high purity oxygen and makes air pressure remain on 1 * 10
-2About pa, heating substrate of strontium titanate to 600～700 ℃, then with the laser pulse ablation lanthanum aluminate target of KrF excimer laser generation, carry out the deposition of lanthanum aluminate film;
Step 4 maintains under depositing temperature and partial pressure of oxygen after deposition finishes and anneals, and after annealing finishes, waits for that sample naturally cools to room temperature, namely obtains the photovoltaic device based on the polar/non-polar heterojunction.
Advantage of the present invention is:
1, simple in structure based on the photovoltaic device of polar/non-polar heterojunction, preparation is easily;
2, the polar material that only deposits several structure cell layers on nonpolar substrate can be realized considerable photovoltaic effect.
Description of drawings
Fig. 1 is the structural representation that the present invention is based on the photovoltaic device of polar/non-polar heterojunction;
Fig. 2 is that the internal electric field that the present invention is based on the photovoltaic device of polar/non-polar heterojunction produces principle schematic;
Fig. 3 is the strontium titanate crystals structural representation that uses according to one embodiment of the invention, and indicates 001 crystal plane direction;
Fig. 4 makes the schematic diagram of electron hole separation according to the internal electric field of the lanthanum aluminate of one embodiment of the invention preparation/strontium titanates heterostructure device;
Fig. 5 is the growth course reflection high energy electron diffraction oscillating curve according to the lanthanum aluminate of one embodiment of the invention preparation/strontium titanates heterostructure device;
Fig. 6 is the atomic force microscope figure according to the lanthanum aluminate of one embodiment of the invention preparation/strontium titanates heterostructure device;
Fig. 7 is the photovoltaic performance test schematic diagram according to one embodiment of the invention lanthanum aluminate/strontium titanates heterostructure device;
Fig. 8 is according to the room temperature photovoltaic effect figure under the lanthanum aluminate of one embodiment of the invention preparation/strontium titanates heterostructure device illumination.
Embodiment
For making the purpose, technical solutions and advantages of the present invention clearer, below in conjunction with specific embodiment, and with reference to accompanying drawing, the present invention is described in more detail.
Fig. 1 is the structural representation that the present invention is based on the photovoltaic device of polar/non-polar heterojunction, as shown in Figure 1, according to an aspect of the present invention, provide a kind of photovoltaic device based on the polar/non-polar heterojunction, this photovoltaic device comprises nonpolar layer and polar layer, wherein:
Described nonpolar layer is for using the substrate of non-polar material;
Described polar layer is the polar material film that is deposited on described nonpolar layer.
Described non-polar material is such as the strontium titanates that can stop for the monohapto of titanyl layer, described polar material is such as being lanthanum aluminate or bismuth ferrite, when described polar material was considered as the atomic layer stacking provisions on specific direction, these atomic layers were alternately with positive and negative electrostatic charge.
For described device, described polar material can provide internal electric field, and this electric field is strong and stable.When there was illumination in the external world, described device absorbed photon and produces photo-generated carrier, and they are separated under the internal electric field effect of polar material: move to the low direction of electromotive force in the hole, and electronics moves to the high direction of electromotive force, thereby demonstrates obvious photovoltaic effect.
Interface manufacture surface electrode and hearth electrode at described device surface and bi-material can be collected these charge carriers, can observe photovoltaic effect.And in above-mentioned this structure, polarity and non-polar material are combined, can cause because polarity is discontinuous electronics reconstruct, thereby at the two-dimensional electron gas of generation at the interface of bi-material, and this two-dimensional electron gas can be directly as natural hearth electrode; Perhaps some non-polar material because self can conduct electricity, can be observed photovoltaic effect for making hearth electrode easily.
As shown in Figure 2, the generation principle of described internal electric field is: after being deposited on polar material on non-polar material, because non-polar material is electric neutrality, and polar material is because of himself structure, in structure cell, the positive and negative electrostatic charge layer that replaces can appear, thereby make in material to occur that electric field is periodically arranged and without the electric field layer, and these directions of an electric field are consistent, so just formed internal electric field.
In one embodiment of this invention, the strontium titanates of the crystal plane direction 001 of stopping take the monohapto of titanyl layer is as substrate, crystal plane direction as shown in Figure 3, deposit lanthanum aluminate thereon, thereby obtain the photovoltaic device of lanthanum aluminate/strontium titanates heterostructure, this device provides internal electric field by the lanthanum aluminate film layer, when there is illumination in the external world, internal electric field can make light activated electronics and hole separate, thereby the photovoltaic effect of showing, as shown in Figure 4, and because polarity is discontinuous, can cause that electronics reconstruct at the generation of interfaces two-dimensional electron gas, can be used as natural hearth electrode.In this embodiment, described lanthanum aluminate film is along crystal plane direction 001 growth of strontium titanates the lanthanum oxygen layer (LaO) that replaces
+Layer and alumina layer (AlO
2)
-The structure of layer stacking, described lanthanum aluminate film thickness is 5 structure cell layers, corresponding to 1.9 nanometers.
According to a further aspect in the invention, provide a kind of preparation method of the photovoltaic device based on the polar/non-polar heterojunction, the method comprises the following steps:
Step 2, the substrate of strontium titanate after cleaning with the corrosion of hydrofluoric acid cushioning liquid be after a period of time, such as about 10 minutes, obtains the substrate of strontium titanate of the crystal plane direction 001 that the monohapto of titanyl layer stop; In an atmospheric oxygen atmosphere, the substrate of strontium titanate that the titanyl layer monohapto after etching stopped is heated to 900～1000 ℃ of annealing (optimum is 950 ℃) afterwards, and annealing time is 2 hours;
Wherein, described hydrofluoric acid cushioning liquid is made into by hydrogen fluoride, ammonium fluoride and deionized water mixing, and the hydrofluoric acid pH value of buffer solution of preparing is about 5.4.
Step 3, the vacuum coating of the substrate of strontium titanate after lanthanum aluminate target and processing being put into pulsed laser deposition (PLD) equipment is indoor, is evacuated to high vacuum state (such as 5 * 10 with mechanical pump and the molecular pump back end vacuum that vacuum coating is indoor
-6Pa) after, pass into high purity oxygen and make air pressure remain on 1 * 10
-2The Pa left and right, heating substrate of strontium titanate to 600～700 ℃ (optimum is 650 ℃), use again KrF excimer laser (Coherent COMPEX Pro201,248nm, 20ns FWHM) the laser pulse ablation lanthanum aluminate target that produces, carry out the deposition of lanthanum aluminate film, in deposition process, available reflection high energy electron diffraction instrument (RHEED) is monitored, wherein, the thickness of described lanthanum aluminate film is 1.9nm, target-substrate distance is 60mm, and the beam spot diameter, of laser beam on target is about 1.5mm, and laser repetition rate is controlled at 1Hz.
Step 4 maintains under depositing temperature and partial pressure of oxygen after deposition finishes and anneals, and annealing time is 1 hour; After annealing finishes, wait for that sample naturally cools to room temperature, namely obtain having the lanthanum aluminate of photovoltaic effect/strontium titanates heterojunction device.
After making this photovoltaic device based on the polar/non-polar heterojunction of lanthanum aluminate/strontium titanates, with spot welding machine, aluminum steel is clicked and entered interface and two-dimensional electron gas connection by film surface, just form hearth electrode; Make surface electrode at film surface by steaming gold, as shown in Figure 6, thereby just completed the preparation of electrode.
Described lanthanum aluminate/strontium titanates heterostructure device sample topography can be observed by atomic force microscope (AFM), and take Keithley6220 as current source, Keithley6514 is that voltmeter is measured its photovoltaic effect, and light source is provided by middle section golden source 185nm low pressure mercury lamp.
The RHEED oscillating curve of lanthanum aluminate film growth course in Fig. 5, reflects the lanthanum aluminate film that has deposited 5 structure cell layers on substrate of strontium titanate 5 cycles of oscillation as shown in Figure 5; The surface topography that film surface is observed under AFM can be seen significantly " step " as shown in Figure 6 from Fig. 6; The photovoltaic performance test philosophy figure of described device as shown in Figure 7, test result as shown in Figure 8: in room temperature, under 29 milliwatts/square centimeter UV-irradiation, the open circuit photovoltage of device is 0.32V, and short-circuit photocurrent is 174nA, and fill factor, curve factor is 41%.
Above-described specific embodiment; purpose of the present invention, technical scheme and beneficial effect are further described; institute is understood that; the above is only specific embodiments of the invention; be not limited to the present invention; within the spirit and principles in the present invention all, any modification of making, be equal to replacement, improvement etc., within all should being included in protection scope of the present invention.
Claims (10)
1. the photovoltaic device based on the polar/non-polar heterojunction, is characterized in that, this photovoltaic device comprises nonpolar layer and polar layer, wherein:
Described nonpolar layer is for using the substrate of non-polar material;
Described polar layer is the polar material film that is deposited on described nonpolar layer.
2. photovoltaic device according to claim 1, is characterized in that, described non-polar material is the strontium titanates that the monohapto of titanyl layer stops.
3. photovoltaic device according to claim 1, is characterized in that, described polar material is lanthanum aluminate or bismuth ferrite.
4. photovoltaic device according to claim 1, is characterized in that, when described polar material was considered as the atomic layer stacking provisions on specific direction, these atomic layers were alternately with positive and negative electrostatic charge.
5. photovoltaic device according to claim 1, it is characterized in that, described polar material provides stronger and stable internal electric field, when there is illumination in the external world, described photovoltaic device absorbs photon and produces photo-generated carrier, they are separated under the internal electric field effect of polar material: move to the low direction of electromotive force in the hole, and electronics moves to the high direction of electromotive force, thereby demonstrate obvious photovoltaic effect.
6. photovoltaic device according to claim 5, is characterized in that, can collect these charge carriers at interface manufacture surface electrode and the hearth electrode of described photovoltaic device surface and bi-material, thus the photovoltaic effect of observing.
7. photovoltaic device according to claim 6, it is characterized in that, described polar material and non-polar material are combined, cause electronics reconstruct because polarity is discontinuous, thereby at the two-dimensional electron gas of generation at the interface of bi-material, and this two-dimensional electron gas can be directly as natural hearth electrode.
8. photovoltaic device according to claim 5, it is characterized in that, after being deposited on polar material on non-polar material, because non-polar material is electric neutrality, and polar material is because of himself structure, the positive and negative electrostatic charge layer that replaces can occur in structure cell, occurs in polar material that electric field is periodically arranged and without the electric field layer thereby make, and these directions of an electric field are consistent, thereby form described internal electric field.
9. the preparation method based on the photovoltaic device of polar/non-polar heterojunction, is characterized in that, the method comprises the following steps:
Step 1 is put into isopropyl alcohol successively with the substrate of strontium titanate of crystal plane direction 001 and deionized water carries out the ultrasonic cleaning processing;
Step 2, the substrate of strontium titanate after cleaning with the corrosion of hydrofluoric acid cushioning liquid be after a period of time, obtains the substrate of strontium titanate of the crystal plane direction 001 that the monohapto of titanyl layer stop; In an atmospheric oxygen atmosphere, the substrate of strontium titanate that the titanyl layer monohapto after etching stopped is heated to 900～1000 ℃ of annealing afterwards, and annealing time is 2 hours;
Step 3, the vacuum coating of the substrate of strontium titanate after lanthanum aluminate target and processing being put into pulsed laser deposition equipment is indoor, after being evacuated to high vacuum state with mechanical pump and the molecular pump back end vacuum that vacuum coating is indoor, passing into high purity oxygen and makes air pressure remain on 1 * 10
-2About pa, heating substrate of strontium titanate to 600～700 ℃, then with the laser pulse ablation lanthanum aluminate target of KrF excimer laser generation, carry out the deposition of lanthanum aluminate film;
Step 4 maintains under depositing temperature and partial pressure of oxygen after deposition finishes and anneals, and after annealing finishes, waits for that sample naturally cools to room temperature, namely obtains the photovoltaic device based on the polar/non-polar heterojunction.
10. preparation method according to claim 9, is characterized in that, described hydrofluoric acid cushioning liquid comprises hydrogen fluoride, ammonium fluoride and deionized water, and its pH value is about 5.4.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111599878A (en) * | 2019-10-16 | 2020-08-28 | 江苏科技大学 | Monocrystalline cuprous oxide nano generator based on crystal face junction and manufacturing method thereof |
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Application publication date: 20130522 |