CN101697354A - Transparent extended p-n heterojunction thin film and preparation method thereof - Google Patents
Transparent extended p-n heterojunction thin film and preparation method thereof Download PDFInfo
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- CN101697354A CN101697354A CN200910236143A CN200910236143A CN101697354A CN 101697354 A CN101697354 A CN 101697354A CN 200910236143 A CN200910236143 A CN 200910236143A CN 200910236143 A CN200910236143 A CN 200910236143A CN 101697354 A CN101697354 A CN 101697354A
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Abstract
The invention discloses a transparent extended p-n heterojunction thin film and a preparation method thereof. The thin film comprises a SrTiO3, a LaxSr1-xSnO3 extended thin film, and any one of the following two extended thin films: a PbZr0.52Ti0.48O3 extended thin film and a BiFeO3 extended thin film, wherein the SrTiO3 is used as a mono-crystal substrate, the LaxSr1-xSnO3 extended thin film is arranged above the mono-crystal substrate and x is not less than 0.03 but is not more than 0.07, and the PbZr0.52Ti0.48O3 extended thin film and the BiFeO3 extended thin film is arranged above the LaxSr1-xSnO3 extended thin film. In the p-n heterojunction thin film provided by the invention, every layer thin film has better mono-crystal extensionality and is of a perovskite structure, the p-n heterojunction thin film not only has better rectification characteristic, but also has high penetration rate within the optical wavelength range of 400-2500 nm (p layer is PZT) and 500-2500 nm (p layer is BFO) of the whole device; the P layer materials (PZT, BFO) are ferroelectric material at the same time, wherein the BFP has both ferroelectricity and antiferromagnetism and has larger potential in the application of semiconductor device.
Description
Technical field
The invention belongs to the monocrystal thin films technical field of electronic devices, particularly a kind of transparent extended p-n heterojunction thin film and preparation method thereof.
Background technology
According to " semiconductor device: physics and technology " the 2nd edition (Semiconductor Devices:Physics andTechnology, 2nd ed.) (S.M.Size, Wiley, New, York, 2002) to introduce, the preparation of semiconductor device and research have had the history in 125 years, from beginning in 1998, be that the electronics industry of basic core has developed into worldwide largest industry with semiconductor device.Nearly 60 kinds of main antetype devices and kind more than 100 device of deriving is designed and creates, and in these devices, p-n junction and heterojunction are 2 kinds of the most basic unit and parts.
(Nature 389 according to Britain's " nature " magazine, 907-908,1997) and U.S.'s " science " magazine (Science300,1245-1246,2003) report, conductivity, while that transparent conductive oxide (TCO) film had both had on the electricity also have the transparency on the optical visual, make transparent circuitry on military affairs, industry and civil use industry great application prospect be arranged.
According to U.S.'s " applied physics wall bulletin " (Appl.Phys.Lett.92,102113,2008) report, because perovskite structure oxide has abundant physical property (as: ferroelectricity, ferromagnetism etc.), based on the p-n heterojunction of perovskite structure huge application potential and obtained broad research in technical field of semiconductor device.
So the transparent epitaxial film p-n heterojunction for preparing high-quality and have a perovskite structure is for exploring and development of new semiconductor film membrane module has important practical significance.
(Nature 389 according to Britain's " nature ", 939-942,1997) report, p type conductive semiconductor material is a lot, but p type transparent conductive material is very deficient, up to now, the TCO film that drops into production application is n N-type semiconductor N film substantially entirely, in the application of semiconductor device can only as passive device as: optical coating or transparency electrode are used.Therefore, the p type TCO material of searching excellent performance has crucial meaning for the real semiconductor transparent devices of preparation.
According to U.S.'s " applied physics wall bulletin " (Appl.Phys.Lett.83,5506-5508,2003) report, the lead zirconate titanate (PbZr of perovskite structure
0.52Ti
0.48O
3, i.e. PZT) and ferroelectric thin film is because its great application prospect in non-volatile dynamic ferroelectric memory is goed deep into broad research.According to U.S.'s " science " magazine (Science 299,1719-1722,2003) report, the ferrous acid bismuth (BiFeO of perovskite structure
3, i.e. BFO) at room temperature have the material of many iron property (having ferroelectricity and anti-ferromagnetic simultaneously) and enjoy researcher in the world to pay close attention to because be at present unique one.
According to the U.S. " physics comment B " (Phys.Rew.B, 59,11257-11266,1999) and " applied physics wall bulletin " (Appl.Phys.Lett.92,102113-102115) report is when the thickness of ferroelectric thin film (as PZT and BFO) is reduced to certain degree, owing to reasons such as oxygen room and ions diffusion, its inside exists bigger carrier concentration, can be regarded p N-type semiconductor N film.
According to the U.S. " solid-state physics (a) " (Phys.Stat.Sol. (a), 71 (1), 1982,13-41), " materialogy wall bulletin " (Materials Letters, 29,255-258,1996) and " Applied Physics A " (Apll.Phys.A, 69,93-96,1999) report, tin-doped indium oxide In2O3:Sn (ITO), the TCO film that antimony-doped tin oxide SnO2:Sb (ATO) and aluminium-doped zinc oxide ZnO:Al (AZO) etc. have been widely used in actual production at present can obtain high transmitance and conductivity at visible region, but can not carry out mutual epitaxial growth and other reason (as: few price height of indium abundance with other monocrystal thin films owing to having polycrystalline or non crystalline structure, it is serious etc. that ITO absorbs in the green-blue light district) limited these application of TCO material in the semiconductor film membrane module.
According to U.S.'s " applied physics wall bulletin " (Appl.Phys.Lett.83,1869,2003), (Appl.Phys.Lett.86,203501,2005) and (Appl.Phys.Lett.92,102113,2008) report, some p-n hetero-junction thin-film devices of bibliographical information have good rectification characteristic at present, the perovskite structure that also has extension simultaneously.But these p-n heterojunction all are single thin film structures, and thin film and the single crystalline substrate of promptly growing formed the p-n heterojunction; Simultaneously the thin-film material great majority of selecting for use in these devices do not have the transparency as: (Appl.Phys.Lett.83,1869,2003) and (Appl.Phys.Lett.92,102113,2008).These deficiencies have limited the range of application of these devices.
In sum, select for use suitable TCO material very important for the transparent p-n heterojunction for preparing the full perovskite structure of extension.Ferrous acid bismuth (BiFeO
3, i.e. BFO) and be a kind of novel magneto-electric functional material of finding in recent years, the preparation window of its film is narrow and small, condition is harsh, only has few group can obtain the single crystal epitaxial film of pure phase and excellent performance in the world.At transparent strontium titanates (SrTiO
3, i.e. STO) and epitaxially grown novel TCO material lanthanum mixes on the single crystalline substrate substrate stronitum stannate (La
xSr
1-xSnO
3, 0.03≤x≤0.07, i.e. LSSO) and film, have perovskite structure, also have high transmission rate simultaneously, more do not appear in the newspapers.The n layer adopts LSSO, and the p layer adopts the extended p-n heterojunction thin film device of PZT or BFO more not appear in the newspapers.
Summary of the invention
The purpose of this invention is to provide a kind of transparent extended p-n heterojunction thin film and preparation method thereof.
Transparent extended p-n heterojunction thin film provided by the invention comprises the SrTiO as the single crystalline substrate substrate
3With the La that is positioned on the described single crystalline substrate substrate
xSr
1-xSnO
3Epitaxial film and be positioned at described La
xSr
1-xSnO
3In following two epitaxial films on the epitaxial film any one: PbZr
0.52Ti
0.48O
3Epitaxial film and BiFeO
3Epitaxial film; Described La
xSr
1-xSnO
3In the epitaxial film, 0.03≤x≤0.07.
In the above-mentioned transparent extended p-n heterojunction thin film, described La
xSr
1-xSnO
3The thickness of epitaxial film is the 50-150 nanometer, PbZr
0.52Ti
0.48O
3The thickness of epitaxial film is the 10-30 nanometer, BiFeO
3The thickness of epitaxial film is the 50-300 nanometer.
The method of the above-mentioned transparent extended p-n heterojunction thin film of preparation provided by the invention comprises the steps:
1) utilize pulse laser sediment method at SrTiO
3Deposit La on the single crystalline substrate substrate
xSr
1-xSnO
3Epitaxial film; Described La
xSr
1-xSnO
3In the epitaxial film, 0.03≤x≤0.07;
2) at described La
xSr
1-xSnO
3On the epitaxial film, continue deposition PbZr
0.52Ti
0.48O
3Epitaxial film or BiFeO
3Epitaxial film obtains transparent extended p-n heterojunction thin film provided by the invention.
In this method, in the described pulse laser sediment method, range of laser energy is 170-210mJ, specifically can be 170-190mJ or 190-210mJ, and frequency is 5-10Hz, specifically can be 5-8Hz or 8-10Hz, and deposition atmosphere is an oxygen;
Described deposition La
xSr
1-xSnO
3During epitaxial film, depositing temperature 650-750 ℃, specifically can be 650-690 ℃ or 690-750 ℃, oxygen is pressed to 15-30Pa, specifically can be 15-20Pa or 20-30Pa; Described La
xSr
1-xSnO
3The thickness of epitaxial film is the 50-150 nanometer;
Described deposition PbZr
0.52Ti
0.48O
3During epitaxial film, depositing temperature is 650-700 ℃, specifically can be 650-690 ℃ or 690-700 ℃, and oxygen is pressed to 20-30Pa, specifically can be 20-25Pa or 25-30Pa, described PbZr
0.52Ti
0.48O
3The thickness of epitaxial film is the 10-30 nanometer;
Described deposition BiFeO
3During epitaxial film, depositing temperature is 650-730 ℃, specifically can be 650-690 ℃ or 690-730 ℃, and oxygen is pressed to 7-15Pa, specifically can be 7-12Pa or 12-15pa, described BiFeO
3The thickness of epitaxial film is the 50-300 nanometer.
Deposition La
xSr
1-xSnO
3Epitaxial film, PbZr
0.52Ti
0.48O
3Epitaxial film and BiFeO
3During epitaxial film, required La
xSr
1-xSnO
3, PbZr
0.52Ti
0.48O
3And BiFeO
3Target all prepares according to solid reaction process.
Described La
xSr
1-xSnO
3Target is prepared according to following steps: is (1-x): x with strontium carbonate, lanthana and tin oxide according to the mol ratio of strontium element, lanthanum element and tin element wherein: 1 mixing obtains described La after the calcining
xSr
1-xSnO
3Target; Wherein, 0.03≤x≤0.07; The temperature of calcining is 1400-1600 ℃, and the time of calcining is 10-15 hour;
Described PbZr
0.52Ti
0.48O
3Target is prepared according to following steps: is 1.1-1.2 with lead oxide, zirconium dioxide and titanium dioxide according to the mol ratio of lead element, zr element and titanium elements wherein: 0.52: 0.48 mixing obtains described PbZr after the calcining
0.52Ti
0.48O
3Target; The temperature of calcining is 900-1250 ℃, and the time of calcining is 2-4 hour;
Described BiFeO
3Target is prepared according to following steps: is 1.1-1.2 with bismuth oxide and iron oxide according to the mol ratio of bismuth element and ferro element wherein: 1 mixing obtains described BiFeO after the calcining
3Target; The temperature of calcining is 750-850 ℃, and the time of calcining is 2-4 hour.
In addition, after deposition step was finished, it was constant to keep oxygen to press, and is cooled to room temperature and takes out described La
xSr
1-xSnO
3Epitaxial film, PbZr
0.52Ti
0.48O
3Epitaxial film and BiFeO
3Epitaxial film.
The present invention has the following advantages:
1, the preparation method of transparent extended p-n heterojunction provided by the invention, the electrically conducting transparent that be widely used (TCO) material traditional with adopting ITO, ATO etc. compared as the p-n heterojunction of n layer material preparation, because TCO material such as ITO is under the situation that keeps high light transmittance and conductivity, prior art can only be carried out the preparation of polycrystalline and amorphous, and PZT, BFO film can not epitaxial growth be prepared into the bright epitaxial film p-n heterojunction of full impregnated on films such as ITO; And the n layer material LSSO that the present invention adopts has perovskite structure, utilize method epitaxial growth LSSO film on the STO single crystalline substrate of pulsed laser deposition (PLD), on the LSSO film, utilize the method for PLD to prepare PZT, BFO film again, because LSSO and PZT, BFO have perovskite structure and cell parameter coupling, so can be prepared into high-quality transparent extended p-n heterojunction.
2, the present invention adopts the LSSO film as n layer, PZT or the BFO double-layer film structure as the p layer, compare with the single thin film structure (promptly utilizing substrate one deck) that present most of p-n film heterojunctions adopt as the p-n heterojunction, the single thin film structure need have specific (special) requirements to the electric property of substrate in the prior art, and double-decker provided by the invention does not have specific (special) requirements to the electrical property of substrate, range of application is more extensive, is more conducive to the integrated application in semiconductor device.
3, the n section bar material LSSO of the present invention's employing has high optical transmittance, be consistent in the light district of 400-2500nm scope with the STO substrate, make entire device in optical wavelength 400-2500nm (the p layer is PZT), 500-2500nm (the p layer is BFO) scope, have high transmitance.Have now and have perovskite structure and the epitaxially grown p-n film heterojunction (as: strontium titanates (Nb:SrTO that the n layer adopts niobium to mix
3) or p layer rice La
0.67Ca
0.33MnO
3Deng), though can epitaxial growth and have perovskite structure, its light transmittance is too low, can't be prepared into transparent devices.Thereby transparent extended p-n heterojunction thin film provided by the invention has extraordinary application prospect in field of semiconductor devices.
4, the p section bar material BFO that adopts of the present invention is a kind of recently by the extensive concern new function material, but that the optimization of its film prepares window is narrow and small, the condition harshness.Preparation method provided by the invention has realized for the first time on LSSO film growing high-quality and has obtained the BFO epitaxial film of good physical property.
Description of drawings
Fig. 1 is substrate base with STO and is the n layer with LSSO that PZT is that the transmitance of p-n hetero-junction thin-film in optical wavelength 300-2500nm scope of p layer characterizes for what embodiment of the invention 1-3 provided.
Fig. 2 is substrate base with STO and is the n layer with LSSO that BFO is that the transmitance of p-n hetero-junction thin-film in optical wavelength 300-2500nm scope of p layer characterizes for what embodiment of the invention 4-6 provided.
The X-ray diffraction structural characterization of the p-n hetero-junction thin-film of the PZT/LSSO/STO structure that Fig. 3 provides for embodiment of the invention 1-3.
The X-ray diffraction structural characterization of the p-n hetero-junction thin-film of the BFO/LSSO/STO structure that Fig. 4 provides for embodiment of the invention 4-6.
The I-V rectification characteristic curve of the p-n hetero-junction thin-film of the PZT/LSSO/STO structure that Fig. 5 provides for embodiment of the invention 1-3.
The I-V rectification characteristic curve of the p-n hetero-junction thin-film of the BFO/LSSO/STO structure that Fig. 6 provides for the embodiment of the invention 4.
The I-V rectification characteristic curve of the p-n hetero-junction thin-film of the BFO/LSSO/STO structure that Fig. 7 provides for the embodiment of the invention 5.
The I-V rectification characteristic curve of the p-n hetero-junction thin-film of the BFO/LSSO/STO structure that Fig. 8 provides for embodiment of the invention 4-6.
The ferroelectric hysteresis loop of the p-n hetero-junction thin-film of the Pt/PZT/LSSO/STO structure that Fig. 9 provides for embodiment of the invention 1-3.
The ferroelectric hysteresis loop of the p-n hetero-junction thin-film of the Pt/BFO/LSSO/STO structure that Figure 10 provides for the embodiment of the invention 6.
Embodiment
Introduce the present invention in detail below in conjunction with the drawings and the specific embodiments: but following embodiment only limits to explain the present invention; protection scope of the present invention should comprise the full content of claim, and promptly can realize the full content of claim of the present invention by following examples those skilled in the art.
Among the following embodiment, in the pulse laser sediment method, used laser is star (ThinFilmStar) the KrF excimer laser of the film of Tuilaser company production, and wavelength is 248nm, beats in the energy density of rotating on the target to be about 3J/cm2.Before deposition step begins, earlier used target is fixed on the target position in PLD system vacuum chamber, with high temperature rapid-curing cutback elargol single crystalline substrate is bonded on the vacuum chamber stainless steel heated sample dish, the distance of adjusting between substrate and the target is 5cm, and the atmosphere of vacuum chamber is high purity oxygen gas.
The p-n hetero-junction thin-film of embodiment 1, preparation PZT/LSSO/STO structure
1) utilizing pulse laser sediment method is 690 ℃ for 190mJ, laser frequency for 5Hz, depositing temperature at laser energy on STO single crystalline substrate substrate, and oxygen is pressed under the condition of 20pa and deposited, and obtaining deposit thickness is the LSSO epitaxial film of 100nm; Described La
xSr
1-xSnO
3In the epitaxial film, x=0.03.
Wherein, required LSSO target during preparation LSSO epitaxial film is prepared according to following method: with strontium titanates SrCO
3(purity 〉=99%) powder, lanthana La
2O
3(deliquescence easily takes place in purity 〉=99.99%, lanthana in air, for ensuring the quality of products accurately, will be in high temperature furnace before using drying 2 hours more than 500 ℃) powder and tin oxide SnO
2(purity 〉=99.8%) powder is according to La
0.03Sr
0.97SnO
3Chemical molar ratio be configured, fully grind it mixed; Be in the high temperature Muffle furnace of air in atmosphere then, respectively calcine 12 hours 1 time at 1200 ℃ and 1350 ℃ respectively that each calcining finishes the back sample powder and all will fully grind 2 hours once more; Powder after the grinding is pressed into the circular piece target under 40 MPa pressure, in the high temperature Muffle furnace, calcined 12 hours for 1450 ℃ then, and sinter molding obtains the LSSO polycrystal target.
2) on described LSSO epitaxial film, in laser frequency is that 10Hz, depositing temperature are that 690 ℃, oxygen are pressed under the condition of 30Pa and deposited, obtaining deposit thickness is the PZT epitaxial film of 20nm, after deposition finishes, oxygen pressure drop under the maintenance preparation condition is to room temperature, take out, promptly obtain transparent epitaxial PZT/LSSO/STOp-n hetero-junction thin-film provided by the invention.
Wherein, the required PZT target of preparation PZT epitaxial film is prepared according to following method: with lead oxide PbO (purity 〉=99%) powder, zirconium dioxide ZrO
2(purity 〉=99%) powder and titanium dioxide TiO
2(purity 〉=99.99%) powder is according to PbZr
0.52Ti
0.48O
3Chemical molar ratio be configured, wherein because the high-temperature volatile of PbO, excessive 15% mass ratio during configuration.The powder that configures will fully grind it is mixed; In atmosphere is 750 ℃ of calcinings 2 hours in the high temperature Muffle furnace of air, fully grinds 2 hours once more after the taking-up, is pressed into disk sheet target then under 40 MPa pressure, and putting into the high temperature Muffle furnace is the PZT target in 2 hours sinter moldings of 1000 ℃ of calcinings.Because the high-temperature volatile of PbO, the temperature rate of sintering should not be too slow.The calcination atmosphere of high temperature Muffle furnace is air.
Light transmission to the p-n heterojunction is that light transmission rate characterizes.
At first test the see through characteristic of STO single crystalline substrate, and then test the light transmission features of whole p-n heterojunction device, as shown in Figure 1 in this scope in the 300-2500nm optical wavelength range.Because the STO single crystalline substrate is single face mechanical polishing, another side is bonded on the stainless steel heated tray with elargol in the process of deposit film, utilizes the order number manually to polish greater than 2500 abrasive paper for metallograph to this face.Among Fig. 1, curve A and curve C are the light transmission rate of STO single crystalline substrate, in the scope of 400-2400nm, all (it is emphasized that the substrate single face manually polishes greater than 60%, the actual light transmittance of STO will be much larger than 60%), near the 360nm wavelength, the STO substrate has individual ABSORPTION EDGE, and the transmitance of light drops to 0 rapidly.Curve B among Fig. 1 is for being the integral light-transmitting rate curve of structure with PZT/LSSO/STO, the concussion that curve B causes for the thickness interference effect of light owing to film.For characterizing the transparency of the core devices of getting rid of substrate effect, represent light transmittance with T, T
PZT/LSSO=T
B/ T
AP-n heterojunction PZT/LSSO at 400-2400nm at the light transmittance of 500-2400nm all greater than 90%.
To the p-n heterojunction structure is that the epitaxial relationship of monocrystalline characterizes.
Is epitaxially grown mono-crystalline structures in order to characterize the p-n junction film with respect to substrate, the X-ray diffraction that device carries out is tested, as shown in Figure 3.At first use X ray θ-2 θ linked scan PZT/LSSO/STO, the interval be 20 spend to 50 the degree, from left to right, diffraction maximum 1,2,3 is represented (001) diffraction maximum of PZT, LSSO, STO respectively among the figure; Diffraction maximum 4,5,6 is represented (002) diffraction maximum of PZT, LSSO, STO respectively.The θ of X-ray diffraction-2 θ linked scan result does not have other diffraction maximum to occur, and has shown that pzt thin film and LSSO film all are pure phase and well epitaxial growth.Insertion portion among Fig. 3 is the result's (being swing curve) to sample X ray ω scanning, and diffraction maximum 7,8,9 is represented the swing curve of (002) diffraction maximum of PZT, LSSO, STO respectively, and corresponding peak position halfwidth is 0.094 degree, 0.057 degree, 0.028 degree.Illustrated that pzt thin film and LSSO film all have good monocrystalline.
Rectification characteristic to the p-n heterojunction characterizes.
Curve E is PZT/La among Fig. 5
0.03Sr
0.97SnO
3The rectification curve chart of p-n heterojunction.As seen from the figure, to show good rectification characteristic: PZT/LSSO be 1.7 * 10 in the commutating ratio of ± 1.3V to thin-film device
3, forward cut-in voltage and reverse breakdown voltage be respectively 0.9V and-3.1V.
Ferroelectric properties to p layer ferroelectric material characterizes.
PZT itself is a kind of ferroelectric material, in order to characterize its ferroelectricity, plates platinum Pt electrode on the p-n junction device, is configured to the film capacitor that structure is Pt/PZT/LSSO/STO, then to its carry out ferroelectric property measurement.Fig. 9 is the electric hysteresis loop of this ferroelectric condenser, (being polarization intensity-electric field strength) non-linear relation curve.Saturated electric hysteresis loop has proved that pzt thin film has ferroelectricity in the prepared device.
In sum, by x ray structure analysis and optical measurement as can be seen, the present invention utilizes the method for pulsed deposition, preparation with LSSO as the n layer, not only epitaxial growth is on the STO single crystalline substrate mutually as the p-n heterojunction of p layer for PZT, and entire device has very high light transmittance at 400-2400 (PZT/LSSO) simultaneously; It can also be seen that by electrical measurement the present invention has good rectification characteristic, therefore will have very big using value in the bright circuit of full impregnated, the p layer material of device has ferroelectricity simultaneously makes its application prospect more extensive.
The p-n hetero-junction thin-film of embodiment 2, preparation PZT/LSSO/STO structure
1) utilizing pulse laser sediment method is 650 ℃ for 170mJ, laser frequency for 8Hz, depositing temperature at laser energy on STO single crystalline substrate substrate, and oxygen is pressed under the condition of 15pa and deposited, and obtaining deposit thickness is the LSSO epitaxial film of 100nm; Described La
xSr
1-xSnO
3In the epitaxial film, x=0.05.
Wherein, required LSSO target during preparation LSSO epitaxial film is prepared according to following method: with strontium titanates SrCO
3(purity 〉=99%) powder, lanthana La
2O
3(deliquescence easily takes place in purity 〉=99.99%, lanthana in air, for ensuring the quality of products accurately, will be in high temperature furnace before using drying 2 hours more than 500 ℃) powder and tin oxide SnO
2(purity 〉=99.8%) powder is according to La
0.05Sr
0.95SnO
3Chemical molar ratio be configured, fully grind it mixed; Be in the high temperature Muffle furnace of air in atmosphere then, respectively calcine 12 hours 1 time at 1200 ℃ and 1350 ℃ respectively that each calcining finishes the back sample powder and all will fully grind 2 hours once more; Powder after the grinding is pressed into the circular piece target under 40 MPa pressure, in the high temperature Muffle furnace, calcined 12 hours for 1450 ℃ then, and sinter molding obtains the LSSO polycrystal target.
2) on described LSSO epitaxial film, in laser frequency is that 8Hz, depositing temperature are that 650 ℃, oxygen are pressed under the condition of 20Pa and deposited, obtaining deposit thickness is the PZT epitaxial film of 10nm, after deposition finishes, oxygen pressure drop under the maintenance preparation condition is to room temperature, take out, promptly obtain transparent epitaxial PZT/LSSO/STOp-n hetero-junction thin-film provided by the invention.
Wherein, preparation PZT epitaxial film required PZT target is that the method according to embodiment 1 is prepared.
Light transmission to the p-n heterojunction is that light transmission rate characterizes.
At first test the see through characteristic of STO single crystalline substrate, and then test the light transmission features of whole p-n heterojunction device, as shown in Figure 1 in this scope in the 300-2500nm optical wavelength range.Because the STO single crystalline substrate is single face mechanical polishing, another side is bonded on the stainless steel heated tray with elargol in the process of deposit film, utilizes the order number manually to polish greater than 2500 abrasive paper for metallograph to this face.Among Fig. 1, curve A and curve C are the light transmission rate of STO single crystalline substrate, in the scope of 400-2400nm, all (it is emphasized that the substrate single face manually polishes greater than 60%, the actual light transmittance of STO will be much larger than 60%), near the 360nm wavelength, the STO substrate has individual ABSORPTION EDGE, and the transmitance of light drops to 0 rapidly.Curve B among Fig. 1 is for being the integral light-transmitting rate curve of structure with PZT/LSSO/STO, the concussion that curve B causes for the thickness interference effect of light owing to film.For characterizing the transparency of the core devices of getting rid of substrate effect, represent light transmittance with T, T
PZT/LSSO=T
B/ T
AP-n heterojunction PZT/LSSO at 400-2400nm at the light transmittance of 500-2400nm all greater than 90%.
To the p-n heterojunction structure is that the epitaxial relationship of monocrystalline characterizes.
Is epitaxially grown mono-crystalline structures in order to characterize the p-n junction film with respect to substrate, the X-ray diffraction that device carries out is tested, as shown in Figure 3.At first use X ray θ-2 θ linked scan PZT/LSSO/STO, the interval be 20 spend to 50 the degree, from left to right, diffraction maximum 1,2,3 is represented (001) diffraction maximum of PZT, LSSO, STO respectively among the figure; Diffraction maximum 4,5,6 is represented (002) diffraction maximum of PZT, LSSO, STO respectively.The θ of X-ray diffraction-2 θ linked scan result does not have other diffraction maximum to occur, and has shown that pzt thin film and LSSO film all are pure phase and well epitaxial growth.Insertion portion among Fig. 3 is the result's (being swing curve) to sample X ray ω scanning, and diffraction maximum 7,8,9 is represented the swing curve of (002) diffraction maximum of PZT, LSSO, STO respectively, and corresponding peak position halfwidth is 0.094 degree, 0.057 degree, 0.028 degree.Illustrated that pzt thin film and LSSO film all have good monocrystalline.
Rectification characteristic to the p-n heterojunction characterizes.
Curve F is PZT/La among Fig. 5
0.05Sr
0.95SNO
3The rectification curve chart of p-n heterojunction.As seen from the figure, thin-film device shows good rectification characteristic.PZT/LSSO is 1.7 * 10 in the commutating ratio of ± 1.3V
4, forward cut-in voltage and reverse breakdown voltage be respectively 0.9V and-2.5V.To be to open the trend that after-current rises faster with 3% difference of mixing,
Ferroelectric properties to p layer ferroelectric material characterizes.
PZT itself is a kind of ferroelectric material, in order to characterize its ferroelectricity, plates platinum Pt electrode on the p-n junction device, is configured to the film capacitor that structure is Pt/PZT/LSSO/STO, then to its carry out ferroelectric property measurement.Fig. 9 is the electric hysteresis loop of this ferroelectric condenser, (being polarization intensity-electric field strength) non-linear relation curve.Saturated electric hysteresis loop has proved that pzt thin film has ferroelectricity in the prepared device.
In sum, by x ray structure analysis and optical measurement as can be seen, the present invention utilizes the method for pulsed deposition, preparation with LSSO as the n layer, not only epitaxial growth is on the STO single crystalline substrate mutually as the p-n heterojunction of p layer for PZT, and entire device has very high light transmittance at 400-2400 (PZT/LSSO) simultaneously; It can also be seen that by electrical measurement the present invention has good rectification characteristic, therefore will have very big using value in the bright circuit of full impregnated, the p layer material of device has ferroelectricity simultaneously makes its application prospect more extensive.
The p-n hetero-junction thin-film of embodiment 3, preparation PZT/LSSO/STO structure
1) utilizing pulse laser sediment method is 750 ℃ for 210mJ, laser frequency for 10Hz, depositing temperature at laser energy on STO single crystalline substrate substrate, and oxygen is pressed under the condition of 30pa and deposited, and obtaining deposit thickness is the LSSO epitaxial film of 150nm; Described La
xSr
1-xSnO
3In the epitaxial film, x=0.07.
Wherein, required LSSO target during preparation LSSO epitaxial film is prepared according to following method: with strontium titanates SrCO
3(purity 〉=99%) powder, lanthana La
2O
3(deliquescence easily takes place in purity 〉=99.99%, lanthana in air, for ensuring the quality of products accurately, will be in high temperature furnace before using drying 2 hours more than 500 ℃) powder and tin oxide SnO
2(purity 〉=99.8%) powder is according to La
0.07Sr
0.93SnO
3Chemical molar ratio be configured, fully grind it mixed; Be in the high temperature Muffle furnace of air in atmosphere then, respectively calcine 12 hours 1 time at 1200 ℃ and 1350 ℃ respectively that each calcining finishes the back sample powder and all will fully grind 2 hours once more; Powder after the grinding is pressed into the circular piece target under 40 MPa pressure, in the high temperature Muffle furnace, calcined 12 hours for 1450 ℃ then, and sinter molding obtains the LSSO polycrystal target.
2) on described LSSO epitaxial film, in laser frequency is that 10Hz, depositing temperature are that 700 ℃, oxygen are pressed under the condition of 25Pa and deposited, obtaining deposit thickness is the PZT epitaxial film of 30nm, after deposition finishes, oxygen pressure drop under the maintenance preparation condition is to room temperature, take out, promptly obtain transparent epitaxial PZT/LSSO/STOp-n hetero-junction thin-film provided by the invention.
Wherein, preparation PZT epitaxial film required PZT target is that the method according to embodiment 1 is prepared.
Light transmission to the p-n heterojunction is that light transmission rate characterizes.
At first test the see through characteristic of STO single crystalline substrate, and then test the light transmission features of whole p-n heterojunction device, as shown in Figure 1 in this scope in the 300-2500nm optical wavelength range.Because the STO single crystalline substrate is single face mechanical polishing, another side is bonded on the stainless steel heated tray with elargol in the process of deposit film, utilizes the order number manually to polish greater than 2500 abrasive paper for metallograph to this face.Among Fig. 1, curve A and curve C are the light transmission rate of STO single crystalline substrate, in the scope of 400-2400nm, all (it is emphasized that the substrate single face manually polishes greater than 60%, the actual light transmittance of STO will be much larger than 60%), near the 360nm wavelength, the STO substrate has individual ABSORPTION EDGE, and the transmitance of light drops to 0 rapidly.Curve B among Fig. 1 is for being the integral light-transmitting rate curve of structure with PZT/LSSO/STO, the concussion that curve B causes for the thickness interference effect of light owing to film.For characterizing the transparency of the core devices of getting rid of substrate effect, represent light transmittance with T, T
PZT/LSSO=T
B/ T
AP-n heterojunction PZT/LSSO at 400-2400nm at the light transmittance of 500-2400nm all greater than 90%.
To the p-n heterojunction structure is that the epitaxial relationship of monocrystalline characterizes.
Is epitaxially grown mono-crystalline structures in order to characterize the p-n junction film with respect to substrate, the X-ray diffraction that device carries out is tested, as shown in Figure 3.At first use X ray θ-2 θ linked scan PZT/LSSO/STO, the interval be 20 spend to 50 the degree, from left to right, diffraction maximum 1,2,3 is represented (001) diffraction maximum of PZT, LSSO, STO respectively among the figure; Diffraction maximum 4,5,6 is represented (002) diffraction maximum of PZT, LSSO, STO respectively.The θ of X-ray diffraction-2 θ linked scan result does not have other diffraction maximum to occur, and has shown that pzt thin film and LSSO film all are pure phase and well epitaxial growth.Insertion portion among Fig. 3 is the result's (being swing curve) to sample X ray ω scanning, and diffraction maximum 7,8,9 is represented the swing curve of (002) diffraction maximum of PZT, LSSO, STO respectively, and corresponding peak position halfwidth is 0.094 degree, 0.057 degree, 0.028 degree.Illustrated that pzt thin film and LSSO film all have good monocrystalline.
Rectification characteristic to the p-n heterojunction characterizes.
Curve G is PZT/La among Fig. 5
0.07Sr
0.93SnO
3The rectification curve chart of p-n heterojunction.As seen from the figure, thin-film device shows good rectification characteristic.PZT/LSSO is 2 * 10 in the commutating ratio of ± 1.3V
3, forward cut-in voltage and reverse breakdown voltage be respectively 0.9V and-2.0V and 5% similar forward open after-current and rise very fast.
Ferroelectric properties to p layer ferroelectric material characterizes.
PZT itself is a kind of ferroelectric material, in order to characterize its ferroelectricity, plates platinum Pt electrode on the p-n junction device, is configured to the film capacitor that structure is Pt/PZT/LSSO/STO, then to its carry out ferroelectric property measurement.Fig. 9 is the electric hysteresis loop of this ferroelectric condenser, (being polarization intensity-electric field strength) non-linear relation curve.Saturated electric hysteresis loop has proved that pzt thin film has ferroelectricity in the prepared device.
In sum, by x ray structure analysis and optical measurement as can be seen, the present invention utilizes the method for pulsed deposition, preparation with LSSO as the n layer, not only epitaxial growth is on the STO single crystalline substrate mutually as the p-n heterojunction of p layer for PZT, and entire device has very high light transmittance at 400-2400 (PZT/LSSO) simultaneously; It can also be seen that by electrical measurement the present invention has good rectification characteristic, therefore will have very big using value in the bright circuit of full impregnated, the p layer material of device has ferroelectricity simultaneously makes its application prospect more extensive.
The p-n hetero-junction thin-film of embodiment 4, preparation BFO/LSSO/STO structure
1) utilizing pulse laser sediment method is 690 ℃ for 190mJ, laser frequency for 5Hz, depositing temperature at laser energy on STO single crystalline substrate substrate, and oxygen is pressed under the condition of 20pa and deposited, and obtaining deposit thickness is the LSSO epitaxial film of 100nm.Described La
xSr
1-xSnO
3In the epitaxial film, x=0.07.
Wherein, the required LSSO target of preparation LSSO epitaxial film is to be prepared according to the method that embodiment 3 provides
2) on described LSSO epitaxial film, in laser frequency is that 10Hz, depositing temperature are that 690 ℃, oxygen are pressed under the condition of 15Pa and deposited, obtaining deposit thickness is the BFO epitaxial film of 50nm, after deposition finishes, oxygen pressure drop under the maintenance preparation condition is to room temperature, take out, promptly obtain transparent epitaxial BFO/LSSO/STOp-n hetero-junction thin-film provided by the invention.
Wherein, the required BFO target of preparation BFO epitaxial film is prepared according to following method: with bismuth oxide Bi
2O
3(purity 〉=99%) powder and iron oxide Fe
2O
3(purity 〉=99%) powder is according to BiFeO
3Chemical molar ratio be configured, wherein because Bi
2O
3High-temperature volatile, excessive 20% mass ratio during configuration.The powder that configures will fully grind it is mixed; Calcined 2 hours for 650 ℃ in the high temperature Muffle furnace, fully ground 2 hours once more after the taking-up, be pressed into disk sheet target then under 40 MPa pressure, putting into the high temperature Muffle furnace is the BFO target in 2 hours sinter moldings of 810 ℃ of calcinings.Because Bi
2O
3High-temperature volatile, the temperature rate of sintering should not be too slow.
Light transmission to the p-n heterojunction is that light transmission rate characterizes.
At first test the see through characteristic of STO single crystalline substrate, and then test the light transmission features of whole p-n heterojunction device, as shown in Figure 2 in this scope in the 300-2500nm optical wavelength range.Because the STO single crystalline substrate is single face mechanical polishing, another side is bonded on the stainless steel heated tray with elargol in the process of deposit film, so utilize abrasive paper for metallograph (the order number is greater than 2500) manually to polish to this face.Among Fig. 2, curve A and curve C are the light transmission rate of STO single crystalline substrate, in the scope of 400-2400nm, all (it is emphasized that the substrate single face manually polishes greater than 60%, the actual light transmittance of STO will be much larger than 60%), near the 360nm wavelength, the STO substrate has individual ABSORPTION EDGE, and the transmitance of light drops to 0 rapidly.Curve D among Fig. 2 is for being the integral light-transmitting rate curve of structure with BFO/LSSO/STO.The concussion that curve B and D all cause for the thickness interference effect of light owing to film.For characterizing the transparency of the core devices of getting rid of substrate effect, we represent light transmittance with T, T
BFO/LSSO=T
D/ T
CP-n heterojunction BFO/LSSO at the light transmittance of 500-2400nm all greater than 90%.
To the p-n heterojunction structure is that the epitaxial relationship of monocrystalline characterizes.
Is epitaxially grown mono-crystalline structures in order to characterize the p-n junction film with respect to substrate, the X-ray diffraction that device carries out is tested, as shown in Figure 4, at first use X ray θ-2 θ linked scan BFO/LSSO/STO, the interval be 20 spend to 50 the degree, from left to right, diffraction maximum 10,11,12 is represented (001) diffraction maximum of LSSO, BFO, STO respectively among the figure; Diffraction maximum 13,14,15 is represented (002) diffraction maximum of LSSO, BFO, STO respectively.The θ of X-ray diffraction-2 θ linked scan result does not have other diffraction maximum to occur, and has shown that BFO film and LSSO film all are pure phase and well epitaxial growth.Insertion portion among Fig. 4 is the result's (being swing curve) to sample X ray ω scanning, diffraction maximum 16,17,18 is represented the swing curve of (002) diffraction maximum of LSSO, BFO, STO respectively, and corresponding peak position halfwidth is 0.216 degree, 0.060 degree, 0.028 degree.Illustrated that BFO film and LSSO film all have good monocrystalline.
Rectification characteristic to the p-n heterojunction characterizes.
Fig. 6 is the rectification curve chart of BFO/LSSO p-n heterojunction.As shown in Figure 6, thin-film device all shows good rectification characteristic.BFO/LSSO is 10 in the commutating ratio of ± 1V, forward cut-in voltage and reverse breakdown voltage be respectively 0.3V and-1V.
Ferroelectric properties to p layer ferroelectric material characterizes.
BFO itself is a kind of ferroelectric material, in order to characterize its ferroelectricity, is plating platinum Pt top electrode on the p-n junction device, is configured to the film capacitor that structure is Pt/BFO/LSSO/STO, then to its carry out ferroelectric property measurement.Fig. 8 is the electric hysteresis loop of this ferroelectric condenser, i.e. polarization intensity-electric field strength) the non-linear relation curve.Saturated electric hysteresis loop has proved that the BFO film has ferroelectricity in the prepared device.
In sum, by x ray structure analysis and optical measurement as can be seen, the present invention utilizes the method for pulsed deposition, preparation with LSSO as the n layer, not only epitaxial growth is on the STO single crystalline substrate mutually as the p-n heterojunction of p layer for BFO, and entire device has very high light transmittance at 500-2400nm (BFO/LSSO) simultaneously; It can also be seen that by electrical measurement the present invention has good rectification characteristic, therefore in the bright circuit of full impregnated, will have very big using value.The p layer material of device has ferroelectricity simultaneously makes its application prospect more extensive.
The p-n hetero-junction thin-film of embodiment 5, preparation BFO/LSSO/STO structure
1) utilizing pulse laser sediment method is 650 ℃ for 170mJ, laser frequency for 8Hz, depositing temperature at laser energy on STO single crystalline substrate substrate, and oxygen is pressed under the condition of 15pa and deposited, and obtaining deposit thickness is the LSSO epitaxial film of 100nm; Described La
xSr
1-xSnO
3In the epitaxial film, x=0.07.
Wherein, the required LSSO target of preparation LSSO epitaxial film is to be prepared according to the method that embodiment 3 provides.
2) on described LSSO epitaxial film, in laser frequency is that 5Hz, depositing temperature are that 650 ℃, oxygen are pressed under the condition of 7Pa and deposited, obtaining deposit thickness is the BFO epitaxial film of 150nm, after deposition finishes, oxygen pressure drop under the maintenance preparation condition is to room temperature, take out, promptly obtain transparent epitaxial BFO/LSSO/STOp-n hetero-junction thin-film provided by the invention.
Wherein, the required BFO target of preparation BFO epitaxial film is to be prepared according to the method that embodiment 4 provides.
Light transmission to the p-n heterojunction is that light transmission rate characterizes.
At first test the see through characteristic of STO single crystalline substrate, and then test the light transmission features of whole p-n heterojunction device, as shown in Figure 2 in this scope in the 300-2500nm optical wavelength range.Because the STO single crystalline substrate is single face mechanical polishing, another side is bonded on the stainless steel heated tray with elargol in the process of deposit film, so utilize abrasive paper for metallograph (the order number is greater than 2500) manually to polish to this face.Among Fig. 2, curve A and curve C are the light transmission rate of STO single crystalline substrate, in the scope of 400-2400nm, all (it is emphasized that the substrate single face manually polishes greater than 60%, the actual light transmittance of STO will be much larger than 60%), near the 360nm wavelength, the STO substrate has individual ABSORPTION EDGE, and the transmitance of light drops to 0 rapidly.Curve D among Fig. 2 is for being the integral light-transmitting rate curve of structure with BFO/LSSO/STO.The concussion that curve B and D all cause for the thickness interference effect of light owing to film.For characterizing the transparency of the core devices of getting rid of substrate effect, we represent light transmittance with T, T
BFO/LSSO=T
D/ T
CP-n heterojunction BFO/LSSO at the light transmittance of 500-2400nm all greater than 90%.
To the p-n heterojunction structure is that the epitaxial relationship of monocrystalline characterizes.
Is epitaxially grown mono-crystalline structures in order to characterize the p-n junction film with respect to substrate, the X-ray diffraction that device carries out is tested, as shown in Figure 4, at first use X ray θ-2 θ linked scan BFO/LSSO/STO, the interval be 20 spend to 50 the degree, from left to right, diffraction maximum 10,11,12 is represented (001) diffraction maximum of LSSO, BFO, STO respectively among the figure; Diffraction maximum 13,14,15 is represented (002) diffraction maximum of LSSO, BFO, STO respectively.The θ of X-ray diffraction-2 θ linked scan result does not have other diffraction maximum to occur, and has shown that BFO film and LSSO film all are pure phase and well epitaxial growth.Insertion portion among Fig. 4 is the result's (being swing curve) to sample X ray ω scanning, diffraction maximum 16,17,18 is represented the swing curve of (002) diffraction maximum of LSSO, BFO, STO respectively, and corresponding peak position halfwidth is 0.216 degree, 0.060 degree, 0.028 degree.Illustrated that BFO film and LSSO film all have good monocrystalline.
Rectification characteristic to the p-n heterojunction characterizes.
Fig. 7 is the rectification curve chart of BFO/LSSO p-n heterojunction.As shown in Figure 7, thin-film device all shows good rectification characteristic.BFO/LSSO is 100 in the commutating ratio of ± 1.3V, forward cut-in voltage and reverse breakdown voltage be respectively 0.3V and-3V.
Ferroelectric properties to p layer ferroelectric material characterizes.
BFO itself is a kind of ferroelectric material, in order to characterize its ferroelectricity, is plating platinum Pt top electrode on the p-n junction device, is configured to the film capacitor that structure is Pt/BFO/LSSO/STO, then to its carry out ferroelectric property measurement.Fig. 8 is the electric hysteresis loop of this ferroelectric condenser, i.e. polarization intensity-electric field strength) the non-linear relation curve.Saturated electric hysteresis loop has proved that the BFO film has ferroelectricity in the prepared device.
In sum, by x ray structure analysis and optical measurement as can be seen, the present invention utilizes the method for pulsed deposition, preparation with LSSO as the n layer, not only epitaxial growth is on the STO single crystalline substrate mutually as the p-n heterojunction of p layer for BFO, and entire device has very high light transmittance at 500-2400nm (BFO/LSSO) simultaneously; It can also be seen that by electrical measurement the present invention has good rectification characteristic, therefore in the bright circuit of full impregnated, will have very big using value.The p layer material of device has ferroelectricity simultaneously makes its application prospect more extensive.
The p-n hetero-junction thin-film of embodiment 6, preparation BFO/LSSO/STO structure
1) utilizing pulse laser sediment method is 730 ℃ for 210mJ, laser frequency for 5Hz, depositing temperature at laser energy on STO single crystalline substrate substrate, and oxygen is pressed under the condition of 30pa and deposited, and obtaining deposit thickness is the LSSO epitaxial film of 100nm; Described La
xSr
1-xSnO
3In the epitaxial film, x=0.07.
Wherein, the required LSSO target of preparation LSSO epitaxial film is to be prepared according to the method that embodiment 3 provides.
2) on described LSSO epitaxial film, in laser frequency is that 10Hz, depositing temperature are that 730 ℃, oxygen are pressed under the condition of 12Pa and deposited, obtaining deposit thickness is the BFO epitaxial film of 300nm, after deposition finishes, oxygen pressure drop under the maintenance preparation condition is to room temperature, take out, promptly obtain transparent epitaxial BFO/LSSO/STO p-n hetero-junction thin-film provided by the invention.
Wherein, the required BFO target of preparation BFO epitaxial film is to be prepared according to the method that embodiment 4 provides.
Light transmission to the p-n heterojunction is that light transmission rate characterizes.
At first test the see through characteristic of STO single crystalline substrate, and then test the light transmission features of whole p-n heterojunction device, as shown in Figure 2 in this scope in the 300-2500nm optical wavelength range.Because the STO single crystalline substrate is single face mechanical polishing, another side is bonded on the stainless steel heated tray with elargol in the process of deposit film, so utilize abrasive paper for metallograph (the order number is greater than 2500) manually to polish to this face.Among Fig. 2, curve A and curve C are the light transmission rate of STO single crystalline substrate, in the scope of 400-2400nm, all (it is emphasized that the substrate single face manually polishes greater than 60%, the actual light transmittance of STO will be much larger than 60%), near the 360nm wavelength, the STO substrate has individual ABSORPTION EDGE, and the transmitance of light drops to 0 rapidly.Curve D among Fig. 2 is for being the integral light-transmitting rate curve of structure with BFO/LSSO/STO.The concussion that curve B and D all cause for the thickness interference effect of light owing to film.For characterizing the transparency of the core devices of getting rid of substrate effect, we represent light transmittance with T, T
BFO/LSSO=T
D/ T
CP-n heterojunction BFO/LSSO at the light transmittance of 500-2400nm all greater than 90%.
To the p-n heterojunction structure is that the epitaxial relationship of monocrystalline characterizes.
Is epitaxially grown mono-crystalline structures in order to characterize the p-n junction film with respect to substrate, the X-ray diffraction that device carries out is tested, as shown in Figure 4, at first use X ray θ-2 θ linked scan BFO/LSSO/STO, the interval be 20 spend to 50 the degree, from left to right, diffraction maximum 10,11,12 is represented (001) diffraction maximum of LSSO, BFO, STO respectively among the figure; Diffraction maximum 13,14,15 is represented (002) diffraction maximum of LSSO, BFO, STO respectively.The θ of X-ray diffraction-2 θ linked scan result does not have other diffraction maximum to occur, and has shown that BFO film and LSSO film all are pure phase and well epitaxial growth.Insertion portion among Fig. 4 is the result's (being swing curve) to sample X ray ω scanning, diffraction maximum 16,17,18 is represented the swing curve of (002) diffraction maximum of LSSO, BFO, STO respectively, and corresponding peak position halfwidth is 0.216 degree, 0.060 degree, 0.028 degree.Illustrated that BFO film and LSSO film all have good monocrystalline.
Rectification characteristic to the p-n heterojunction characterizes.
Fig. 8 is the rectification curve chart of BFO/LSSO p-n heterojunction.As shown in Figure 8, thin-film device all shows good rectification characteristic.BFO/LSSO is 100 in the commutating ratio of ± 2V, forward cut-in voltage and reverse breakdown voltage be respectively 0.3V and-4V, better than the rectification effect of 50nm.
Ferroelectric properties to p layer ferroelectric material characterizes.
BFO itself is a kind of ferroelectric material, in order to characterize its ferroelectricity, is plating platinum Pt top electrode on the p-n junction device, is configured to the film capacitor that structure is Pt/BFO/LSSO/STO, then to its carry out ferroelectric property measurement.Figure 10 is the electric hysteresis loop of this ferroelectric condenser, (being polarization intensity-electric field strength) non-linear relation curve.Saturated electric hysteresis loop has proved that the BFO film has ferroelectricity in the prepared device.
In sum, by x ray structure analysis and optical measurement as can be seen, the present invention utilizes the method for pulsed deposition, preparation with LSSO as the n layer, not only epitaxial growth is on the STO single crystalline substrate mutually as the p-n heterojunction of p layer for BFO, and entire device has very high light transmittance at 500-2400nm (BFO/LSSO) simultaneously; It can also be seen that by electrical measurement the present invention has good rectification characteristic, therefore in the bright circuit of full impregnated, will have very big using value.The p layer material of device has ferroelectricity simultaneously makes its application prospect more extensive.
Claims (7)
1. a transparent extended p-n heterojunction thin film comprises the SrTiO as the single crystalline substrate substrate
3With the La that is positioned on the described single crystalline substrate substrate
xSr
1-xSnO
3Epitaxial film and be positioned at described La
xSr
1-xSnO
3In following two epitaxial films on the epitaxial film any one: PbZr
0.52Ti
0.48O
3Epitaxial film and BiFeO
3Epitaxial film; Described La
xSr
1-xSnO
3In the epitaxial film, 0.03≤x≤0.07.
2. film according to claim 1 is characterized in that: described La
xSr
1-xSnO
3The thickness of epitaxial film is the 50-150 nanometer, PbZr
0.52Ti
0.48O
3The thickness of epitaxial film is the 10-30 nanometer, BiFeO
3The thickness of epitaxial film is the 50-300 nanometer.
3. a method for preparing claim 1 or 2 described transparent extended p-n heterojunction thin films comprises the steps:
1) utilize pulse laser sediment method at SrTiO
3Deposit La on the single crystalline substrate substrate
xSr
1-xSnO
3Epitaxial film; Described La
xSr
1-xSnO
3In the epitaxial film, 0.03≤x≤0.07;
2) at described La
xSr
1-xSnO
3On the epitaxial film, continue to deposit PbZr with pulse laser sediment method
0.52Ti
0.48O
3Epitaxial film or BiFeO
3Epitaxial film obtains claim 1 or 2 described transparent extended p-n heterojunction thin films.
4. method according to claim 3 is characterized in that: in the described pulse laser sediment method, range of laser energy is 170-210mJ, and frequency is 5-10Hz, and deposition atmosphere is an oxygen;
Described deposition La
xSr
1-xSnO
3During epitaxial film, depositing temperature 650-750 ℃, oxygen is pressed and is 15-30Pa, described La
xSr
1-xSnO
3The thickness of epitaxial film is the 50-150 nanometer;
Described deposition PbZr
0.52Ti
0.48O
3During epitaxial film, depositing temperature is 650-700 ℃, and oxygen is pressed and is 20-30Pa, described PbZr
0.52Ti
0.48O
3The thickness of epitaxial film is the 10-30 nanometer;
Described deposition BiFeO
3During epitaxial film, depositing temperature is 650-730 ℃, and oxygen is pressed and is 7-15Pa, described BiFeO
3The thickness of epitaxial film is the 50-300 nanometer.
5. according to claim 3 or 4 described methods, it is characterized in that: deposition La
xSr
1-xSnO
3Epitaxial film, PbZr
0.52Ti
0.48O
3Epitaxial film and BiFeO
3During epitaxial film, required La
xSr
1-xSnO
3, PbZr
0.52Ti
0.48O
3And BiFeO
3Target all prepares according to solid reaction process.
6. method according to claim 5 is characterized in that: described La
xSr
1-xSnO
3Target is prepared according to following steps: is (1-x): x with strontium carbonate, lanthana and tin oxide according to the mol ratio of strontium element, lanthanum element and tin element wherein: 1 mixing obtains described La after the calcining
xSr
1-xSnO
3Target; Wherein, 0.03≤x≤0.07;
Described PbZr
0.52Ti
0.48O
3Target is prepared according to following steps: is 1.1-1.2 with lead oxide, zirconium dioxide and titanium dioxide according to the mol ratio of lead element, zr element and titanium elements wherein: 0.52: 0.48 mixing obtains described PbZr after the calcining
0.52Ti
0.48O
3Target;
Described BiFeO
3Target is prepared according to following steps: is 1.1-1.2 with bismuth oxide and iron oxide according to the mol ratio of bismuth element and ferro element wherein: 1 mixing obtains described BiFeO after the calcining
3Target.
7. method according to claim 6 is characterized in that: preparation La
xSr
1-xSnO
3During target, the temperature of calcining is 1400-1600 ℃, and the time of calcining is 10-15 hour;
Preparation PbZr
0.52Ti
0.48O
3During target, the temperature of calcining is 900-1250 ℃, and the time of calcining is 2-4 hour;
Preparation BiFeO
3During target, the temperature of calcining is 750-850 ℃, and the time of calcining is 2-4 hour.
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| CN108018525A (en) * | 2016-11-01 | 2018-05-11 | 中国科学院上海硅酸盐研究所 | A kind of Bi9Ti3Fe5O27More epitaxial ferroelectric films of stratiform and preparation method thereof |
| CN108018525B (en) * | 2016-11-01 | 2020-01-17 | 中国科学院上海硅酸盐研究所 | Bi9Ti3Fe5O27Laminated multiferroic epitaxial film and preparation method thereof |
| CN108987125A (en) * | 2018-08-13 | 2018-12-11 | 云南大学 | Ca-Ti ore type stannate electrode material for super capacitor with high-specific capacitance super and preparation method thereof |
| CN108987125B (en) * | 2018-08-13 | 2021-04-16 | 云南大学 | Perovskite stannate supercapacitor electrode material, preparation method and application |
| CN110581283A (en) * | 2019-09-19 | 2019-12-17 | 中国科学技术大学 | Bismuth-doped solid oxide cell fuel electrode material and preparation method and application thereof |
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