CN103938156A - Europium doped bismuth ferrite film, preparation method and application thereof - Google Patents
Europium doped bismuth ferrite film, preparation method and application thereof Download PDFInfo
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- CN103938156A CN103938156A CN201410097917.8A CN201410097917A CN103938156A CN 103938156 A CN103938156 A CN 103938156A CN 201410097917 A CN201410097917 A CN 201410097917A CN 103938156 A CN103938156 A CN 103938156A
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- 229910052797 bismuth Inorganic materials 0.000 title claims abstract description 33
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 229910000859 α-Fe Inorganic materials 0.000 title claims abstract description 32
- 229910052693 Europium Inorganic materials 0.000 title claims description 36
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 title claims description 36
- 239000000758 substrate Substances 0.000 claims abstract description 97
- 239000010409 thin film Substances 0.000 claims abstract description 32
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 21
- 239000010703 silicon Substances 0.000 claims abstract description 21
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 19
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims abstract description 19
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 17
- 239000001301 oxygen Substances 0.000 claims abstract description 17
- 230000003287 optical effect Effects 0.000 claims abstract description 15
- 239000011248 coating agent Substances 0.000 claims abstract description 12
- 238000000576 coating method Methods 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 10
- 238000004544 sputter deposition Methods 0.000 claims abstract description 10
- 239000013077 target material Substances 0.000 claims abstract description 9
- 239000010408 film Substances 0.000 claims description 88
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- 239000003599 detergent Substances 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 11
- 238000000151 deposition Methods 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 230000008021 deposition Effects 0.000 claims description 5
- 238000004140 cleaning Methods 0.000 claims description 3
- 238000005477 sputtering target Methods 0.000 claims description 2
- 238000002425 crystallisation Methods 0.000 abstract description 11
- 230000008025 crystallization Effects 0.000 abstract description 11
- 239000002994 raw material Substances 0.000 abstract description 7
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- 238000000427 thin-film deposition Methods 0.000 abstract description 3
- 229910002902 BiFeO3 Inorganic materials 0.000 abstract 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 30
- 239000002253 acid Substances 0.000 description 15
- 229910052759 nickel Inorganic materials 0.000 description 15
- 239000000463 material Substances 0.000 description 14
- 239000007788 liquid Substances 0.000 description 12
- 239000013078 crystal Substances 0.000 description 10
- 229910052761 rare earth metal Inorganic materials 0.000 description 10
- 150000002910 rare earth metals Chemical class 0.000 description 8
- 238000002441 X-ray diffraction Methods 0.000 description 7
- 239000004519 grease Substances 0.000 description 6
- 238000009413 insulation Methods 0.000 description 6
- 238000009434 installation Methods 0.000 description 5
- 230000010287 polarization Effects 0.000 description 5
- 238000004549 pulsed laser deposition Methods 0.000 description 5
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 4
- 238000000089 atomic force micrograph Methods 0.000 description 4
- 230000008033 biological extinction Effects 0.000 description 4
- 229910052709 silver Inorganic materials 0.000 description 4
- 239000004332 silver Substances 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 230000002269 spontaneous effect Effects 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910000416 bismuth oxide Inorganic materials 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- AEBZCFFCDTZXHP-UHFFFAOYSA-N europium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Eu+3].[Eu+3] AEBZCFFCDTZXHP-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 229910002340 LaNiO3 Inorganic materials 0.000 description 1
- 230000010748 Photoabsorption Effects 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000005621 ferroelectricity Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Landscapes
- Physical Vapour Deposition (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
本发明公开了一种铕掺杂的铁酸铋薄膜，其包括以镍酸镧为缓冲层的硅衬底和组成式为Bi1-xEuxFeO3(0≤x≤0.07)的靶材，靶材沉积在衬底上。本发明还公开了铕掺杂的铁酸铋薄膜的制备方法，清洗衬底，将靶材和衬底置于镀膜室内，调节压强至5×10-4Pa以下。以每分钟10℃使衬底升温至700℃；调节使溅射气压为10Pa；在温度700℃、氧压10Pa下保持10分钟。调节使衬底反转，靶材正转；衬底和靶材的距离为6cm。以脉冲激光器进行薄膜沉积60min，保温30min。以每分钟20℃的速度降温，至200℃取出得到铕掺杂的铁酸铋薄膜。本发明的制备方法反应过程易于控制，原料易得。本发明铕掺杂的铁酸铋薄膜的结晶性能、漏电性能明显得到改善，光学带隙变小，提高了BiFeO3薄膜的光伏性能，具有广泛的应用前景。The invention discloses a europium-doped bismuth ferrite thin film, which comprises a silicon substrate with lanthanum nickelate as a buffer layer and a target material whose composition formula is Bi 1-x Eu x FeO 3 (0≤x≤0.07) , the target material is deposited on the substrate. The invention also discloses a preparation method of the europium-doped bismuth ferrite thin film. The substrate is cleaned, the target material and the substrate are placed in a coating chamber, and the pressure is adjusted to be below 5×10 -4 Pa. The temperature of the substrate was raised to 700° C. at 10° C. per minute; the sputtering pressure was adjusted to 10 Pa; the temperature was kept at 700° C. and the oxygen pressure was 10 Pa for 10 minutes. Adjust to make the substrate reverse and the target rotate forward; the distance between the substrate and the target is 6cm. Thin film deposition was performed with a pulsed laser for 60 minutes and kept warm for 30 minutes. The temperature was lowered at a rate of 20° C. per minute, and the europium-doped bismuth ferrite thin film was obtained by taking it out to 200° C. The reaction process of the preparation method of the invention is easy to control, and the raw materials are easy to obtain. The crystallization performance and leakage performance of the europium-doped bismuth ferrite thin film of the invention are obviously improved, the optical band gap becomes smaller, the photovoltaic performance of the BiFeO3 thin film is improved, and the invention has wide application prospects.
Description
Technical field
The present invention relates to ferroelectric and photovoltaic material technical field, specifically propose the bismuth ferrite (BiFeO of a kind of rare earth elements europium (Eu) doping
3) film and its preparation method and application.
Background technology
Sun power is a kind of very important renewable energy source.What at present, can be used as solar energy materials mainly contains several materials such as silicon, III-V compounds of group, copper-indium-galliun-selenium (CIGS), dye sensitization, polymkeric substance.Silica-based solar cell is large-scale production, but its opto-electronic conversion mechanism has determined the light ability generation current that only has energy to surpass band gap, the difficult problem that this has caused sun power to transform: little band-gap energy absorbs more multi-photon, produces larger electric current but under voltage; And the larger voltage electric current of large band-gap energy generation is limited, most of solar photon can not be absorbed, thereby efficiency of conversion is also difficult to obtain very large raising.
Ferroelectrics is a kind of material with spontaneous polarization, and in certain temperature range, a kind of material that its spontaneous polarization moment of dipole can change with external electric field direction.Most of ferroelectric materials have semiconductive and ferroelectricity concurrently, the photoelectric conversion capacity that ferroelectric material has, high output photovoltage, the characteristic of electric field regulation and control photovoltaic, make it at aspects such as ferroelectric photovoltaic cell, CD-ROM driver, optical sensors, have broad application prospects.Ferroelectric spontaneous polarization is attractive for solar cell application, and because positive charge and negative charge for being produced by photoabsorption have the aptitude being separated from each other, this is more efficiently collected them.Regrettably, at ferroelectric material, be used in and in photovoltaic field, face two severe problems: one, ferroelectric material band gap is bigger than normal.Even if can be with minimum bismuth ferrite (BiFeO in ferroelectric material
3), its band gap has also reached 2.8eV.Therefore, existing ferroelectric material conventionally only absorbs and forms a fraction of high-energy photon of solar spectrum.Its two, thin film crystallization is second-rate, causes film easily to leak electricity.
Summary of the invention
, film large for prior art ferroelectric material band gap be the defect such as electric leakage easily, the invention provides the bismuth ferrite (BiFeO that a kind of rare earth elements europium (Eu) adulterates
3) film and preparation method thereof.According to the present invention, can realize preparation can be with and reduce and ferroelectric bismuth ferrite (BiFeO that thin film crystallization quality is obviously improved
3) film, thereby the photovoltaic performance of raising ferroelectric material.The film of preparing by present method, its energy gap is 2.6eV.In the present invention, adopt pulsed laser deposition on the silicon substrate as buffer layer, to prepare film at nickel acid lanthanum, raw materials used cost is low, tests easyly, can effectively rare-earth europium element evenly be mixed, and obtains even compact film, and surface average roughness is about 2.0nm.
According to a first aspect of the invention, the present invention proposes a kind of bismuth ferrite thin film of europium doping, comprises substrate and target, and described target is deposited on described substrate; Wherein, described substrate is to take the silicon substrate that nickel acid lanthanum is buffer layer, and described target composition formula is Bi
1-xeu
xfeO
3, 0≤x≤0.07.According to actual particular case, x=0,0.03,0.05 or 0.07.
According to a second aspect of the invention, the present invention proposes the preparation method of the bismuth ferrite thin film of above-mentioned europium doping, makes the Bi of different Eu elementary compositions by traditional solid phase reaction method
1-xeu
xfeO
3sputtering target material, then utilizes pulsed laser deposition at nickel acid lanthanum (composition formula is LaNiO3), to do on silicon (symbol of element the is Si) substrate of buffer layer and prepares corresponding Bi
1-xeu
xfeO
3film.Preparation method of the present invention specifically comprises the steps:
A) pre-preparation
The Bi that the purity of take is 99.99%
1-xeu
xfeO
3as target, 0≤x≤0.07 wherein; The silicon substrate that the nickel acid lanthanum of usining is made buffer layer is as substrate;
Described substrate is cleaned, described target and described substrate are positioned in coating chamber, regulate coating chamber pressure to 5 * 10
-4below Pa.
Wherein, the substrate of selection is the silicon substrate that nickel acid lanthanum is made buffer layer, by the effect of buffer layer, can make film be grown on substrate well.
B) preparation of the bismuth ferrite thin film of europium doping
To described substrate heating; With 10 ℃ of per minutes, make described substrate be warming up to 700 ℃; Be filled with purity and be 99.99% oxygen, it is 10Pa that adjusting gas flow makes sputtering pressure; 700 ℃ of temperature, oxygen is pressed under 10Pa condition and is kept 10 minutes;
Described substrate reversion, described target forward; The distance that regulates described substrate and described target is 6cm;
Pulsed laser is set, and making laser energy is 200mJ, and laser frequency is 10Hz;
Open described pulsed laser and carry out thin film deposition, depositing time is 60min; Then be incubated 30min;
With the speed cooling of 20 ℃ of per minutes, during to 200 ℃, take out the film sample that deposition obtains, obtain the bismuth ferrite thin film of described europium doping.
Wherein, by making substrate 700 ℃ of temperature, oxygen is pressed under 10Pa condition and is kept substrate 10 minutes, and the defect in substrate is well repaired.
Wherein, by the difference of substrate and target sense of rotation, can obtain the film of even compact.
According to one embodiment of the present invention, with BiFeO
3as target, the silicon substrate that nickel acid lanthanum is made buffer layer is as substrate, and the step of the bismuth ferrite thin film adulterating through pre-preparation, europium also repeats this two steps, obtains the Bi of different europium components
1-xeu
xfeO
3film, wherein x=0,0.03,0.05 or 0.07.
According to another embodiment of the present invention, in the preparation of the bismuth ferrite thin film adulterating at europium, by adjusting the sputter target position in coating chamber, laser energy is focused on different target position, open laser, sputter obtains the Bi of different europium components
1-xeu
xfeO
3film, wherein x=0,0.03,0.05 or 0.07.Wherein, the Bi for preparing different europium components by changing the target of sputter
1-xeu
xfeO
3film.
In the present invention, the raw material of preparing target comprises europium sesquioxide, bismuth oxide and ferric oxide.The preparation process of target is, takes the europium sesquioxide of certain mass with table balance, and bismuth oxide and ferric oxide, then by three kinds of prepared using ball mill ball millings, mix three kinds of raw materials.Again three kinds of raw materials that mix being pressed into diameter with press is 5mm, thickness is the cylindrical of 3mm, finally put it in retort furnace, with the speed of 5 ℃ per hour, heat up, be raised to 780 ℃, in air atmosphere, sintering is two hours, then is down to room temperature with the speed of 5 ℃ per hour, obtains required target.
In the present invention, adopt target that europium doping is different to obtain the Bi of different europium components
1-xeu
xfeO
3film, x=0 wherein, 0.03,0.05,0.07.For example,, with Bi
0.97eu
0.03feO
3as preparation of target materials, obtain Bi
0.97eu
0.03feO
3film, with Bi
0.95eu
0.05feO
3as preparation of target materials, obtain Bi
0.95eu
0.05feO
3film, with Bi
0.93eu
0.07feO
3as preparation of target materials, obtain Bi
0.93eu
0.07feO
3film.
In the present invention, the method for cleaning substrate is, first with liquid detergent, removes grease, then with acetone, removes liquid detergent residual, then puts into the ultrasonic 30min of alcohol, finally puts into after deionized water for ultrasonic 30min and takes out and be stored in spirituous solution.
According to the prepared Bi1 of the inventive method
-xeu
xfeO
3film, along with the increase of Eu element in film, the crystal property of gained film, electric leakage performance are significantly improved, and optical band gap diminishes.Bismuth ferrite thin film (the Bi of rare-earth europium doping of the present invention
1-xeu
xfeO
3film), its photovoltaic performance be improved significantly, be suitable for the application in the devices field such as ferroelectric photovoltaic cell, CD-ROM driver, optical sensor.
Beneficial effect of the present invention comprises, compared with prior art, pulsed laser deposition of the present invention is simple in structure and easy to operate.Meanwhile, target and substrate with different directions rotation, can obtain uniform Bi simultaneously
1-xeu
xfeO
3film; Can pass through underlayer temperature, sputtering pressure and substrate material etc. is controlled surface topography and the crystalline quality of film.
In addition, the pulsed laser deposition technique that utilizes the present invention to adopt, by setting underlayer temperature, sputter oxygen is pressed, and can make the film composition prepared accurate, and crystalline quality is good.By XRD, AFM test, show the Bi that present method prepares
1-xeu
xfeO
3film has high crystalline quality, surfacing, moderate crystal grain size.
Preparation method's reaction process of the present invention is easy to control, and raw material is easy to get.The Bi that the present invention makes
1-xeu
xfeO
3film, along with the raising of europium doped elementary composition, can find out according to the ferroelectric hysteresis loop detecting, electrical properties improves, and band gap reduces, and is conducive to ferroelectric Bi
1-xeu
xfeO
3the application of film in photovoltaic field.
Accompanying drawing explanation
Fig. 1 is the prepared Bi of the embodiment of the present invention 1
1-xeu
xfeO
3the X-ray diffraction figure (XRD) of (wherein x=0,0.03,0.05,0.07) film;
Fig. 2 is the prepared BiFeO of the embodiment of the present invention 1
3the atomic force microscope images of film (AFM);
Fig. 3 is the Bi of the embodiment of the present invention 2
0.97eu
0.03feO
3the atomic force microscope images of film (AFM);
Fig. 4 is the Bi of the embodiment of the present invention 3
0.95eu
0.05feO
3the atomic force microscope images of film (AFM);
Fig. 5 is the Bi of the embodiment of the present invention 4
0.93eu
0.07feO
3the atomic force microscope images of film (AFM);
Fig. 6 is the Bi of the embodiment of the present invention 1 to embodiment 4 preparation
1-xeu
xfeO
3ferroelectric hysteresis loop (P-E) image of (wherein x=0,0.03,0.05,0.07) film;
Fig. 7 is the Bi of the invention process embodiment 1 to embodiment 4 preparation
1-xeu
xfeO
3the optical extinction coefficient image of (wherein x=0,0.03,0.05,0.07) film;
Fig. 8 is the Bi of the invention process embodiment 1 to embodiment 4 preparation
1-xeu
xfeO
3the optical band gap image of (wherein x=0,0.03,0.05,0.07) film.
Embodiment
In conjunction with following specific embodiments and the drawings, the present invention is described in further detail, and protection content of the present invention is not limited to following examples.Do not deviating under the spirit and scope of inventive concept, variation and advantage that those skilled in the art can expect are all included in the present invention, and take appending claims as protection domain.Implement process of the present invention, condition, reagent, experimental technique etc., except the content of mentioning specially below, be universal knowledege and the common practise of this area, the present invention is not particularly limited content.
The preparation method of the bismuth ferrite thin film of the europium doping that the present invention proposes, comprises the steps:
(1) target: selecting purity is 99.99% Bi
1-xeu
xfeO
3target, 0≤x≤0.07.
(2) substrate: the silicon substrate that the nickel acid lanthanum of take is made buffer layer is substrate, first with liquid detergent, remove grease, then with acetone, remove liquid detergent residual, then put into the ultrasonic 30min of alcohol, finally put into after deionized water for ultrasonic 30min and take out and be stored in spirituous solution.
(3) vacuumize: target and substrate are placed in coating chamber, and utilizing mechanical pump and molecular pump that vacuum chamber is evacuated to pressure is 5 * 10
-4below pa.
(4) heated substrate:
Open heating installation, by computer, control substrate is heated by the speed of 10 ℃ of per minute intensifications.
(5) regulate sputtering pressure:
Promote temperature and arrive 700 ℃ of preset values, open oxygen channel, adjustments of gas passes into flow, and then to make sputtering pressure be 10Pa to Molecular regulator pump slide valve, insulation 10min.Meanwhile, regulating the distance of substrate and target is 6cm, substrate base reversion, target forward.
(6) thin film deposition:
Unbalanced pulse laser apparatus, makes single beam laser scioptics focus on Bi with 45° angle
1-xeu
xfeO
3on target, regulate laser energy and laser frequency.Preferably, adjusting laser energy is 200mJ, and adjusting laser frequency is 10Hz, and the distance adjustment of target and substrate is 6em, deposition 60min.
(7) after deposition finishes, insulation 30min.Then make substrate cooling with the speed of 20 ℃ of per minutes.Be cooled to 200 ℃ of following Bi of taking-up
1-xeu
xfeO
3(0≤x≤0.07) film, obtains object product.
Preparation method's raw materials cost of the present invention is low, easy and simple to handle, and the film preparation cycle is short, is applicable to commercially producing requirement.In addition, than other film preparing technologies, utilize pulsed laser deposition, by regulating the oxygen pressure in film deposition process, laser energy, the distance of target position and substrate, can prepare component accurate, the film that crystalline quality is good easily.
The present invention, by rare-earth europium element doping, improves the crystal property of bismuth ferrite thin film, thereby reduces leakage current, and the electric property of bismuth ferrite thin film improves.In addition, europium doping can also reduce the optical band gap of bismuth ferrite thin film, thereby improves the assimilated efficiency of bismuth ferrite to sunlight, improves the photovoltaic performance of bismuth ferrite thin film.
Embodiment 1
(1) selection of target: adopt the BiFeO that purity is 99.99%
3target;
(2) clean the silicon substrate that nickel acid lanthanum is done buffer layer: this substrate can utilize sol-gel method to make on business silicon substrate.First use liquid detergent, remove grease, then with acetone, remove liquid detergent residual, then put into the ultrasonic 30min of alcohol, take out after finally putting into deionized water for ultrasonic 30min;
(3) vacuumize: by BiFeO
3the silicon substrate that target and nickel acid lanthanum are done buffer layer is positioned in coating chamber, and substrate is fixed in substrate disc with silver slurry, and utilizing mechanical pump and molecular pump that vacuum is evacuated to pressure is 5 * 10
-4below Pa;
(4) substrate heating: open heating installation, control with computer, make it with 10 ℃ of intensifications of per minute, be warmed up to 700 ℃;
(5) temperature arrives 700 ℃ of preset values, opens oxygen channel, pours purity and be 99.99% oxygen, adjusting gas flow, and Molecular regulator pump slide valve then, obtaining sputtering pressure is 10Pa, adjusting knob makes substrate base reversion, target forward simultaneously;
(6) unbalanced pulse laser apparatus, laser scioptics focus on BiFeO with 45° angle
3on target, it is 200mJ that laser energy is set, and frequency is 10Hz, and target and substrate distance are 6em, depositing time 60min;
(7) after insulation 30min, substrate is cooled to below 200 ℃ with the speed of 20 ℃ of per minutes, take out BiFeO
3film.
The Bi that the present embodiment prepares
1-xeu
xfeO
3film (wherein x=0), as shown in Figure 1, film has shown obvious preferred orientation (h00) to its XRD figure, shows Bi
1-xeu
xfeO
3thin film crystallization is of high quality.
As shown in Figure 1, this Bi
1-xeu
xfeO
3the crystallization direction of (wherein x=0) film is (h00) crystal orientation substantially.
Be illustrated in figure 2 BiFeO
3the atomic force microscope figure of film, shows the BiFeO that the inventive method prepares
3film crystal grain is larger, is about 125nm, and mean roughness is 5.2nm.
Embodiment 2
(1) selection of target: adopt the Bi that purity is 99.99%
0.97eu
0.03feO
3target;
(2) clean the silicon substrate that nickel acid lanthanum is done buffer layer: first use liquid detergent, remove grease, then with acetone, remove liquid detergent residual, then put into the ultrasonic 30min of alcohol, take out after finally putting into deionized water for ultrasonic 30min;
(3) vacuumize: by Bi
0.97eu
0.03feO
3the silicon substrate that target and nickel acid lanthanum are done buffer layer is positioned in coating chamber, and substrate is fixed in substrate disc with silver slurry, and utilizing mechanical pump and molecular pump that vacuum is evacuated to pressure is 5 * 10
-4below Pa;
(4) substrate heating: open heating installation, control with computer, make it with 10 ℃ of intensifications of per minute, be warmed up to 700 ℃;
(5) temperature arrives preset value, opens oxygen channel, pours purity and be 99.99% oxygen, adjusting gas flow, and Molecular regulator pump slide valve then, obtaining sputtering pressure is 10Pa, adjusting knob makes substrate base reversion, target forward simultaneously;
(6) unbalanced pulse laser apparatus, laser scioptics focus on Bi with 45° angle
0.97eu
0.03feO
3on target, it is 200mJ that laser energy is set, and frequency is 10Hz, and target and substrate distance are 6cm, depositing time 60min;
(7) after insulation 30min, substrate is cooled to below 200 ℃ with the speed of 20 ℃ of per minutes, take out Bi
0.97eu
0.03feO
3film.
The Bi that the present embodiment prepares
1-xeu
xfeO
3film (wherein x=0.03), as shown in Figure 1, film has shown obvious preferred orientation (h00) to its XRD figure, shows Bi
1-xeu
xfeO
3thin film crystallization is of high quality.
As shown in Figure 1, this Bi
1-xeu
xfeO
3the crystallization direction of (wherein x=0.03) film is (h00) crystal orientation substantially.
Be illustrated in figure 3 Bi
0.97eu
0.03feO
3the primary electron force microscope figure of film, shows the Bi that the inventive method prepares
0.97eu
0.03feO
3it is fine and close that film becomes, and mean roughness is 4.1nm.
Embodiment 3
(1) selection of target: adopt the Bi that purity is 99.99%
0.95eu
0.05feO
3target;
(2) clean the silicon substrate that nickel acid lanthanum is done buffer layer: first use liquid detergent, remove grease, then with acetone, remove liquid detergent residual, then put into the ultrasonic 30min of alcohol, take out after finally putting into deionized water for ultrasonic 30min;
(3) vacuumize: by Bi
0.95eu
0.05feO
3the silicon substrate that target and nickel acid lanthanum are done buffer layer is positioned in coating chamber, and substrate is fixed in substrate disc with silver slurry, and utilizing mechanical pump and molecular pump that vacuum is evacuated to pressure is 5 * 10
-4below Pa;
(4) substrate heating: open heating installation, control with computer, make it with 10 ℃ of intensifications of per minute, be warmed up to 700 ℃;
(5) temperature arrives preset value, opens oxygen channel, pours purity and be 99.99% oxygen, adjusting gas flow, and Molecular regulator pump slide valve then, obtaining sputtering pressure is 10Pa, adjusting knob makes substrate base reversion, target forward simultaneously;
(6) unbalanced pulse laser apparatus, laser scioptics focus on Bi with 45° angle
0.95eu
0.05feO
3on target, it is 200mJ that laser energy is set, and frequency is 10Hz, and target and substrate distance are 6cm, depositing time 60min;
(7), after insulation 30min, substrate is cooled to 200 ℃ of following Bi of taking-up with the speed of 20 ℃ of per minutes
0.95eu
0.05feO
3film.
The Bi that the present embodiment prepares
1-xeu
xfeO
3film (wherein x=0.05), as shown in Figure 1, film has shown obvious preferred orientation (h00) to its XRD figure, shows Bi
1-xeu
xfeO
3thin film crystallization is of high quality.
As shown in Figure 1, this Bi
1-xeu
xfeO
3the crystallization direction of (wherein x=0.05) film is (h00) crystal orientation substantially.
Be illustrated in figure 4 Bi
0.95eu
0.05feO
3the primary electron force microscope figure of film, shows the Bi that the inventive method prepares
0.95eu
0.05feO
3film crystal grain diminishes, and is about 100nm, and mean roughness is 3.6nm.
Embodiment 4
(1) selection of target: adopt the Bi that purity is 99.99%
0.93eu
0.07feO
3target;
(2) clean the silicon substrate that nickel acid lanthanum is done buffer layer: first use liquid detergent, remove grease, then with acetone, remove liquid detergent residual, then put into the ultrasonic 30min of alcohol, take out after finally putting into deionized water for ultrasonic 30min;
(3) vacuumize: by Bi
0.93eu
0.07feO
3the silicon substrate that target and nickel acid lanthanum are done buffer layer is positioned in coating chamber, and substrate is fixed in substrate disc with silver slurry, and utilizing mechanical pump and molecular pump that vacuum is evacuated to pressure is 5 * 10
-4below Pa;
(4) substrate heating: open heating installation, control with computer, make it with 10 ℃ of intensifications of per minute, be warmed up to 700 ℃;
(5) temperature arrives preset value, opens oxygen channel, pours purity and be 99.99% oxygen, adjusting gas flow, and Molecular regulator pump slide valve then, obtaining sputtering pressure is 10Pa, adjusting knob makes substrate base reversion, target forward simultaneously;
(6) unbalanced pulse laser apparatus, laser scioptics focus on Bi with 45° angle
0.93eu
0.07feO
3on target, it is 200mJ that laser energy is set, and frequency is 10Hz, and target and substrate distance are 6cm, depositing time 60min;
(7), after insulation 30min, substrate is cooled to 200 ℃ of following BI of taking-up with the speed of 20 ℃ of per minutes
0.93eu
0.07feO
3film.
The Bi that the present embodiment prepares
1-xeu
xfeO
3film (wherein x=0.07), as shown in Figure 1, film has shown obvious preferred orientation (h00) to its XRD figure, shows Bi
1-xeu
xfeO
3thin film crystallization is of high quality.
As shown in Figure 1, this Bi
1-xeu
xfeO
3the crystallization direction of (wherein x=0.07) film is (h00) crystal orientation substantially.
Be illustrated in figure 5 Bi
0.93eu
0.07feO
3the primary electron force microscope figure of film, shows the Bi that the inventive method prepares
0.93eu
0.07feO
3film is finer and close, and surface is more smooth, and mean roughness is reduced to 2.0nm.
To the prepared Bi of above embodiment 1-4
1-xeu
xfeO
3the leakage property that film (wherein x=0,0.03,0.05,0.07) carries out, band gap etc. detect, and result is as shown in Fig. 6-8.
Bi as shown in Figure 6
1-xeu
xfeO
3the ferroelectric hysteresis loop of film (wherein x=0,0.03,0.05,0.07) is visible, and along with the increase of europium doped element, it is large that remnant polarization becomes, and the leakage current of film reduces.
Be illustrated in figure 7 the Bi that elliptically polarized light matching obtains
1-xeu
xfeO
3the optical extinction coefficient image of film (wherein x=0,0.03,0.05,0.07) is visible, along with the increase of europium doped element, and the maximum value generation red shift of optical extinction coefficient k.
Be illustrated in figure 8 the Bi that utilizes optical extinction coefficient to calculate
1-xeu
xfeO
3the optical band gap image of film (wherein x=0,0.03,0.05,0.07) is visible, and along with the increase of europium doped element, the band gap of film reduces.
Visible according to above experimental result, the present invention has improved the photovoltaic performance of bismuth ferrite thin film by introducing rare-earth europium element doping.Along with the increase of Eu element in film, the crystal property of gained film, electric leakage performance obviously improves, and optical band gap diminishes.Along with the increase of rare-earth europium element doping amount, Bi
1-xeu
xfeO
3the mean roughness of film is reduced to 2nm from 5.2nm, illustrates that the doping of rare-earth europium has improved Bi
1-xeu
xfeO
3the crystalline quality of film; Along with the increase of rare-earth europium element doping amount, Bi
1-xeu
xfeO
3the remnant polarization of film is from 2.5uC/cm
-2increase to 7.5uC/cm
-2, Bi is described
1-xeu
xfeO
3the electric property of film improves; Along with the increase of rare-earth europium element doping amount, Bi
1-xeu
xfeO
3the optical band gap of film is reduced to 2.6eV from 2.78eV, and europium element doping can improve Bi
1-xeu
xfeO
3the assimilated efficiency of film to sunlight, thus Bi improved
1-xeu
xfeO
3the photovoltaic performance of film.
As can be seen here, the Bi that the present invention is prepared by europium doped element
1-xeu
xfeO
3film (wherein x=0,0.03,0.05 or 0.07) has been realized and has been significantly improved BiFeO
3the photovoltaic performance of film.
Claims (8)
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| CN201410097917.8A CN103938156B (en) | 2014-03-17 | 2014-03-17 | A kind of bismuth ferrite thin film of europium doping and its preparation method and application |
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| CN104388894A (en) * | 2014-12-09 | 2015-03-04 | 湖北大学 | Method for preparing low-band gap ferroelectric photovoltaic film through pulsed laser deposition |
| CN110791732A (en) * | 2019-11-15 | 2020-02-14 | 福建师范大学 | A kind of preparation method of nickel-doped bismuth ferrite film system material |
| CN111074244A (en) * | 2018-10-19 | 2020-04-28 | 营口理工学院 | Nickel-cerium co-doped bismuth ferrite film material and preparation method thereof |
| CN112921288A (en) * | 2021-01-25 | 2021-06-08 | 齐鲁工业大学 | Preparation of high-energy-storage-density BaTiO3Ferroelectric thin film method, product and application thereof |
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| CN112921288A (en) * | 2021-01-25 | 2021-06-08 | 齐鲁工业大学 | Preparation of high-energy-storage-density BaTiO3Ferroelectric thin film method, product and application thereof |
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|---|---|
| CN103938156B (en) | 2016-06-29 |
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