CN108242395B - Method for epitaxially growing high-quality lead magnesium niobate titanate film on gallium nitride substrate - Google Patents
Method for epitaxially growing high-quality lead magnesium niobate titanate film on gallium nitride substrate Download PDFInfo
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- 229910002601 GaN Inorganic materials 0.000 title claims abstract description 71
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 56
- ZBSCCQXBYNSKPV-UHFFFAOYSA-N oxolead;oxomagnesium;2,4,5-trioxa-1$l^{5},3$l^{5}-diniobabicyclo[1.1.1]pentane 1,3-dioxide Chemical compound [Mg]=O.[Pb]=O.[Pb]=O.[Pb]=O.O1[Nb]2(=O)O[Nb]1(=O)O2 ZBSCCQXBYNSKPV-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 239000000758 substrate Substances 0.000 title claims abstract description 51
- JMASRVWKEDWRBT-UHFFFAOYSA-N Gallium nitride Chemical compound [Ga]#N JMASRVWKEDWRBT-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 238000000034 method Methods 0.000 title claims abstract description 36
- 238000000151 deposition Methods 0.000 claims abstract description 65
- 230000008021 deposition Effects 0.000 claims abstract description 26
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000001301 oxygen Substances 0.000 claims abstract description 23
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 23
- 239000000919 ceramic Substances 0.000 claims abstract description 13
- 238000000137 annealing Methods 0.000 claims abstract description 12
- 238000011065 in-situ storage Methods 0.000 claims abstract description 12
- 239000000126 substance Substances 0.000 claims abstract description 12
- 239000011777 magnesium Substances 0.000 claims abstract description 11
- 239000013077 target material Substances 0.000 claims abstract description 9
- 229910004206 O3-xPbTiO3 Inorganic materials 0.000 claims abstract description 6
- 238000002360 preparation method Methods 0.000 claims abstract description 5
- 150000001875 compounds Chemical class 0.000 claims abstract description 3
- 239000010408 film Substances 0.000 claims description 50
- 239000010409 thin film Substances 0.000 claims description 32
- FOLMBQLGENFKLO-UHFFFAOYSA-N [Pb].[Mg].[Nb] Chemical compound [Pb].[Mg].[Nb] FOLMBQLGENFKLO-UHFFFAOYSA-N 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims 1
- 229910001882 dioxygen Inorganic materials 0.000 claims 1
- 239000010955 niobium Substances 0.000 claims 1
- 239000004065 semiconductor Substances 0.000 description 12
- 238000010304 firing Methods 0.000 description 9
- 238000001228 spectrum Methods 0.000 description 9
- 239000000203 mixture Substances 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 238000004544 sputter deposition Methods 0.000 description 8
- 238000005137 deposition process Methods 0.000 description 7
- 230000010354 integration Effects 0.000 description 7
- 230000010287 polarization Effects 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 239000011812 mixed powder Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 229910052594 sapphire Inorganic materials 0.000 description 3
- 239000010980 sapphire Substances 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- 230000002411 adverse Effects 0.000 description 2
- 229910052454 barium strontium titanate Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005669 field effect Effects 0.000 description 2
- 229910052451 lead zirconate titanate Inorganic materials 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229910004243 O3-PbTiO3 Inorganic materials 0.000 description 1
- 229910004293 O3—PbTiO3 Inorganic materials 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000000407 epitaxy Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- HFGPZNIAWCZYJU-UHFFFAOYSA-N lead zirconate titanate Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ti+4].[Zr+4].[Pb+2] HFGPZNIAWCZYJU-UHFFFAOYSA-N 0.000 description 1
- GQYHUHYESMUTHG-UHFFFAOYSA-N lithium niobate Chemical compound [Li+].[O-][Nb](=O)=O GQYHUHYESMUTHG-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000006855 networking Effects 0.000 description 1
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 238000002128 reflection high energy electron diffraction Methods 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000005533 two-dimensional electron gas Effects 0.000 description 1
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Abstract
The invention relates to a method for epitaxially growing a high-quality lead magnesium niobate titanate film on a gallium nitride substrate, wherein the compound chemical formula of the lead magnesium niobate titanate film is (1-x) Pb (Mg)1/3Nb2/3)O3‑xPbTiO3Wherein x is more than 0 and less than 1, and the preparation method comprises the following steps: (1) taking lead magnesium niobate titanate ceramic as a target material, taking a (0002) oriented gallium nitride film as a substrate, controlling the temperature of the substrate to 700-850 ℃, introducing oxygen and adjusting the oxygen pressure to 0.5-10 Pa; (2) adjusting the laser energy to 2-6 mJ/cm2Firstly, depositing a buffer layer on the (0002) oriented gallium nitride substrate in a mode of increasing the laser frequency in sections, then depositing for 1-3 hours at the laser frequency of 5-10Hz, and then annealing in situ to obtain the lead magnesium niobate titanate film. The invention fills the blank in the field, and the adopted deposition means is simple and easy to implement.
Description
Technical Field
The invention belongs to the technical field of semiconductor films, and particularly relates to a method for epitaxially growing a high-quality lead magnesium niobate titanate film on a (0002) oriented gallium nitride substrate.
Background
Based on the important application of GaN wide bandgap semiconductor in the fields of power electronics, high frequency devices and photoelectronics, people have recently started to pay attention to the integration of ferroelectric thin film and GaN-based semiconductor, aiming at combining the unique functional characteristics of ferroelectric thin film and GaN-based semiconductor to develop a new generation of multifunctional integrated electronic devices. Among them, it is the development direction with the most application potential at present to develop a Ferroelectric field effect High Mobility Transistor (MFSHEMT: Metal-Ferroelectric-Semiconductor High Electron Mobility Transistor) by integrating the Ferroelectric film as a polarization gate dielectric with an AlGaN/GaN-based HEMT device. The principle is that the polarization characteristic of a ferroelectric gate medium is utilized to modulate AlGaN/GaN interface two-dimensional electron gas, and the conversion between depletion and accumulation of current carriers in a channel is accelerated, so that the gate control of a device is enhanced. Through the spontaneous polarization characteristic of regulation and control ferroelectric film inside, offset the piezoelectricity polarization field in the AlGaN, realize the complete depletion to two-dimensional electron in the AlGaN/GaN interface channel, can effectively solve traditional AlGaN/GaN HEMT device in view of the above and can only work in the key problem of depletion type (normally open, the consumption is big, control complicacy) mode, be expected to develop novel high performance enhancement mode (normally closed, the consumption is little, control is simple) AlGaN/GaN HEMT device. The enhancement mode HEMT has incomparable advantages of a depletion mode HEMT, can effectively reduce the complexity and the cost of a high-frequency integrated circuit, effectively improves the safety of a power conversion integrated circuit, and simultaneously effectively reduces the power consumption of the circuit. In recent years, although some techniques are applied to develop an enhancement-type AlGaN/GaN HEMT device, the techniques include reducing the AlGaN barrier thickness, growing nonpolar AlGaN/GaN, adding a p-GaN or InGaN cap layer, etching a recessed gate, and performing fluorine plasma treatment. However, the above-mentioned techniques increase the complexity of the device process, and the obtained device threshold voltage is low (generally lower than 3V), which is not favorable for the device to operate under noise interference. Compared with the traditional enhancement type AlGaN/GaN HEMT technology, the ferroelectric gate dielectric technology has the advantages of simple device structure, controllable threshold voltage, low gate leakage current, high breakdown voltage and the like, and is likely to become the mainstream technology of the enhancement type AlGaN/GaN HEMT in the future.
At present, the integration of ferroelectric thin films and GaN-based semiconductors is still the initial research stage, and the results are rarely reported. And the GaN-based integration related to the ferroelectric thin film also only relates to a few traditional ferroelectric materials, such as lead zirconate titanate (PZT), Barium Strontium Titanate (BST) and lithium niobate (LiNbO)3) And the like. Lead magnesium niobate titanate (Pb (Mg)1/3Nb2/3)O3-PbTiO3PMN-PT) is a solid solution composed of a relaxor ferroelectric PMN and a general ferroelectric PT, and has a high dielectric constant, a large piezoelectric coefficient, and more excellent ferroelectric polarization performance than conventional ferroelectric materials. Based on the analysis, the novel PMN-PT replaces the traditional ferroelectric film and is applied to the gate dielectric of the AlGaN/GaN HEMT, and an enhanced MFSHEMT device with more excellent performance is expected to be developed. In addition, the PMN-PT material has excellent sensing characteristics on physical parameters such as external temperature, electric field, stress, light and the like, and combines the PMN-PT with a GaN-based semiconductor integrated circuitIt is hoped to develop novel intelligent sensor system, has huge application potential in emerging high technology industries such as thing networking, intelligent wearing, intelligent house.
In conclusion, the epitaxial integration of the novel ferroelectric thin film represented by PMN-PT and the GaN-based semiconductor becomes one of the key problems to be solved urgently in the field of integrated ferroelectric electricity, semiconductor power devices and intelligent sensors at present, and has important scientific significance and application value. At present, researches related to PMN-PT/GaN-based epitaxial integration and device application are not reported internationally, and the main bottleneck of the researches is lattice mismatch between cubic phase PMN-PT and hexagonal phase GaN (AlGaN), so that high-quality epitaxial integration between the cubic phase PMN-PT and the hexagonal phase GaN (AlGaN) is very difficult.
Disclosure of Invention
The invention aims to overcome the difficulty caused by epitaxial integration of the lattice mismatch between cubic phase lead magnesium niobate titanate and hexagonal phase gallium nitride and provides a method for extending a high-quality lead magnesium niobate titanate film on a gallium nitride substrate.
On one hand, the invention provides a method for epitaxially growing a high-quality lead magnesium niobate titanate film on a gallium nitride substrate, wherein the compound chemical formula of the lead magnesium niobate titanate film is (1-x) Pb (Mg)1/3Nb2/3)O3-xPbTiO3Wherein 0 < x < 1, preferably 0.3 < x < 0.4, the preparation method comprises:
(1) taking lead magnesium niobate titanate ceramic as a target material, taking a (0002) oriented gallium nitride film as a substrate, controlling the temperature of the substrate to 700-850 ℃, introducing oxygen and adjusting the oxygen pressure to 0.5-10 Pa;
(2) adjusting the laser energy to 2-6 mJ/cm2Firstly, depositing a buffer layer on the (0002) oriented gallium nitride substrate in a mode of increasing the laser frequency in a sectional mode, then depositing for 1-3 hours under the laser frequency of 5-10Hz, and then annealing in situ to obtain the lead magnesium niobate titanate film.
According to the method, the gallium nitride film with the (0002) orientation is selected as the substrate, the temperature of the substrate is controlled to be 700-850 ℃, and the buffer layer is gradually deposited on the gallium nitride substrate with the (0002) orientation in a mode of increasing the laser frequency in a segmented mode, so that the adverse effect on the lead magnesium niobate titanate film, which is generated by lattice mismatch generated between the gallium nitride substrate with the (0002) orientation and the lead magnesium niobate titanate film, is gradually reduced, and the high-quality lead magnesium niobate titanate film is epitaxially deposited on the gallium nitride substrate.
Preferably, the step of depositing the buffer layer by increasing the laser frequency in stages comprises: depositing with 1Hz laser for 1-5 min, then depositing with 2Hz laser for 1-5 min, and then depositing with 3Hz laser for 1-5 min. The buffer layer is deposited by adopting a mode of increasing the laser frequency in a segmented mode, wherein the buffer layer is deposited by changing the laser frequency for three times, and the buffer layer can be deposited on the gallium nitride substrate by being prepared for more than three times, so that the lead magnesium niobate titanate film is finally obtained. However, if the number of steps is small, the buffer layer transition is not smooth enough, and the epitaxial quality is not high. In addition, the buffer layer prepared by the 3-step method is also limited by equipment, the maximum use of the laser adopted by the invention is 10Hz, so the buffer layer is prepared by 1, 2 and 3Hz generally, and the film is deposited by 5-10 Hz. The higher frequency of 4Hz tends to make the buffer layer too thick and is not generally used as a buffer layer.
Preferably, the depositing the buffer layer by increasing the laser frequency in stages includes: the deposition was carried out with a 1Hz laser for 2 minutes, then with a 2Hz laser for 3 minutes and then with a 3Hz laser for 5 minutes.
Preferably, the mixed raw material powder is used for firing the lead magnesium niobate titanate ceramic according to the standard stoichiometric ratio, wherein the lead content is 10-15% higher than that of the standard stoichiometric ratio. Because lead is easy to volatilize in the firing process, the dosage of the lead is higher than the standard stoichiometric dosage when the lead is proportioned, and the purpose is to avoid the deviation of chemical composition in the film growth process.
Preferably, in the step (1), the oxygen pressure is 2 to 6 Pa.
Preferably, in the step (2), the laser energy is 5.5mJ/cm2。
Preferably, in step (2), the in-situ annealing time is 0.5 to 2 hours, preferably 1 hour.
In another aspect, the present invention also provides a gallium nitride-based lead magnesium niobate titanate thin film prepared according to the above method, comprising: comprising a (0002) oriented gallium nitride film, a (111) oriented lead magnesium niobate titanate film epitaxially grown on the gallium nitride film, and a buffer layer between the (0002) oriented gallium nitride film and the (111) oriented lead magnesium niobate titanate film.
Preferably, the thickness of the (111) oriented lead magnesium niobate titanate thin film is 80 to 200 nm. The thickness of the buffer layer is obtained by comparing the number of laser pulses used for depositing the buffer layer during the experiment with the total number of pulses. However, the buffer layer prepared by the method is generally within 5nm in thickness, is smaller than the total thickness of the film, and is difficult to distinguish under the test methods such as a scanning electron microscope, so that the thickness of the whole buffer layer is expressed.
Preferably, the substrate may be a sapphire single crystal flash.
Preferably, the thickness of the (0002) oriented gallium nitride film can be adjusted according to actual needs, for example, 5 microns.
On the other hand, the invention also provides application of the gallium nitride-based lead magnesium niobate titanate film prepared by the method in an intelligent sensor system, in the Internet of things, intelligent wearing and intelligent home.
The invention provides a method for epitaxially growing a high-quality lead magnesium niobate titanate film on a gallium nitride substrate, which fills the blank in the field, the adopted deposition means is simple and easy to implement, the obtained lead magnesium niobate titanate film has the (111) orientation with the largest polarization intensity, and the key problem of preparing a high-performance PMN-PT/GaN-based integrated device is solved.
Drawings
FIG. 1 is a Rhed diagram of the lead magnesium niobate titanate thin film obtained in example 1 at different stages of deposition;
FIG. 2 is an XRD spectrum of the lead magnesium niobate titanate thin film prepared in example 1;
FIG. 3 shows Rhed spectra (a)650 deg.C (b)850 deg.C for samples obtained at two different substrate temperatures for example 3 and comparative example 1.
Detailed Description
The present invention is further illustrated by the following examples, which are to be understood as merely illustrative and not restrictive.
The invention discloses a method for depositing a lead magnesium niobate titanate thin film on a gallium nitride semiconductor thin film substrate with (0002) orientation by using a pulse laser deposition method, namely, the lead magnesium niobate titanate ferroelectric thin film directly grows epitaxially on the gallium nitride semiconductor thin film substrate with (0002) orientation. Wherein the component composite chemical formula of the lead magnesium niobate titanate ferroelectric film is (1-x) Pb (Mg)1/3Nb2/3)O3-xPbTiO3(0 < x < 1, preferably 0.3 < x < 0.4).
The invention relates to an epitaxial growth method of a (111) oriented lead magnesium niobate titanate film on a gallium nitride film substrate. Specifically, the gallium nitride film growing in the sapphire single crystal flash (0002) orientation is selected as the substrate, the adverse effect of lattice mismatch on the film is reduced by adjusting process parameters, the chemical composition deviation in the film growth process is avoided, and the method is the key for realizing the epitaxial deposition of the high-quality lead magnesium niobate titanate film on the gallium nitride substrate. The method for epitaxially growing a high-quality lead magnesium niobate titanate thin film on a gallium nitride substrate provided by the invention is exemplarily described as follows.
And (3) preparing the niobium-magnesium-lead titanate ceramic target. According to the chemical composition (1-x) Pb (Mg)1/3Nb2/3)O3-xPbTiO3(0 < x < 1, preferably 0.3 < x < 0.4), and mixing the raw material powder (e.g. MgO, TiO)2、PbO、Nb2O5Etc.) are mixed and then the niobium-magnesium-lead titanate ceramic target material is fired. The lead is easy to volatilize in the firing process, and the using amount of the lead is 10-15% higher than the standard stoichiometric using amount when the powder is proportioned.
Taking lead magnesium niobate titanate ceramic as a target, heating a gallium nitride substrate (or called gallium nitride film) with (0002) orientation to 700-850 ℃. Then, oxygen is introduced and the pressure of the oxygen is adjusted to 0.5 to 10Pa, preferably 2 to 6 Pa.
After the preparation work is done, the laser energy is adjusted to 2-6 mJ/cm2(preferably 5.5 mJ/cm)2) The buffer layer is initially deposited with a lower laser pulse frequency, i.e. in a stepwise increasing laser frequency. Utensil for cleaning buttockIn particular, it comprises: depositing for 1-5 minutes by using 1Hz laser, then depositing for 1-5 minutes by using 2Hz laser, and then depositing for 1-5 minutes by using 3Hz laser to obtain the buffer layer. It should be noted that the manner of increasing the laser frequency in stages in the present invention includes, but is not limited to, preparing the buffer layer by the above-mentioned three-step method, and the lattice mismatch generated between the (0002) oriented gallium nitride substrate and the lead magnesium niobate titanate thin film can be minimized only by depositing the buffer layer in accordance with the stepwise increase of the laser frequency (at least three steps). As an example, the deposition was performed with a 1Hz laser for 2 minutes, then with a 2Hz laser for 3 minutes, and then with a 3Hz laser for 5 minutes. Then, a film is deposited by using a higher laser frequency, and then the film is deposited for 1 to 3 hours under the laser frequency of 5 to 10Hz, and the deposition is stopped for 2 minutes every 10 minutes in the deposition process. For example, the deposition is carried out for 2 hours at a laser frequency of 5Hz, and the deposition is stopped for 2 minutes every 10 minutes. The thickness of the (111) oriented lead magnesium niobate titanate thin films described in the present invention generally depends on the laser frequency and the total deposition time. The thickness of the lead magnesium niobate titanate film can be 80-200 nm.
And finally, keeping the temperature (700-850 ℃) of the substrate and the pressure (0.5-10 Pa) of the vacuum chamber consistent with those in the deposition process, and annealing in situ for a period of time (the annealing time can be 0.5-2 hours, and is preferably 1 hour).
As an example, the film preparation method is a pulse laser deposition method, and comprises the following steps:
(1) pb (Mg) according to the desired chemical composition (1-x)1/3Nb2/3)O3-xPbTiO3(0 < x < 1, preferably 0.3 < x < 0.4) firing the niobium-magnesium-lead titanate ceramic target material by using the mixed powder, wherein the amount of the mixed powder is 10-15% higher than the standard stoichiometric amount due to easy volatilization of lead in the firing process;
(2) heating the gallium nitride substrate with the orientation of (0002) to 700-850 ℃, introducing oxygen, and adjusting the oxygen pressure to 2-6 Pa;
(3) adjusting the laser energy to 5mJ/cm2；
(4) Depositing for 2min by using 1Hz laser, then depositing for 3min by using 2Hz laser, then depositing for 5min by using 3Hz laser, depositing a buffer layer, and depositing a film by using 5Hz frequency;
(5) the substrate temperature and vacuum chamber pressure were maintained and the in-situ anneal was carried out for 1 hour.
The invention adopts the pulse laser deposition technology, and directly epitaxially grows the (111) oriented lead magnesium niobate titanate film on the (0002) oriented gallium nitride substrate by adjusting target components and a deposition process. The deposition method adopted by the invention is simple and feasible, and the obtained lead magnesium niobate titanate thin film is in the (111) orientation with the maximum polarization strength, thereby solving the key problem of preparing a high-performance PMN-PT/GaN-based ferroelectric-semiconductor integrated device.
The epitaxy of the perovskite ferroelectric film on the gallium nitride substrate is a key technology for realizing the ferroelectric field effect transistor, and has important scientific value and wide application prospect.
The present invention will be described in detail by way of examples. It is also to be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the invention, and that certain insubstantial modifications and adaptations of the invention by those skilled in the art may be made in light of the above teachings. The specific process parameters and the like of the following examples are also only one example of suitable ranges, i.e., those skilled in the art can select the appropriate ranges through the description herein, and are not limited to the specific values exemplified below.
The following embodiments use a (0002) -oriented gallium nitride thin film (5 μm thick) on a sapphire single crystal as a substrate unless otherwise specified.
Example 1
(1) 0.65Pb (Mg) according to chemical composition1/3Nb2/3)O3-0.35PbTiO3Firing the niobium-magnesium-lead titanate ceramic target material by using the mixed powder, wherein the lead dosage is 10% higher than the stoichiometric dosage;
(2) heating the gallium nitride substrate with the orientation of (0002) to 800 ℃, introducing oxygen, and adjusting the oxygen pressure to 6 Pa;
(3) the laser energy is adjusted to 5.5mJ/cm2；
(4) And (3) sputtering deposition process: depositing for 2 minutes by using 1Hz laser, then depositing for 3 minutes by using 2Hz laser, then depositing for 5 minutes by using 3Hz laser, then keeping the 5Hz deposition, stopping for 2 minutes every 10 minutes, and sputtering for 2 hours;
(5) keeping the substrate temperature at 800 ℃ and the oxygen pressure at 6Pa, and annealing in situ for 1 hour.
FIG. 1 is a Rhed spectrum of a lead magnesium niobate titanate thin film at various stages of deposition, wherein FIG. 1(a) is the Rhed spectrum of a gallium nitride substrate before deposition, FIG. 1(b) is the Rhed spectrum after 5 minutes of deposition with a 3Hz laser, FIG. 1(c) is the Rhed spectrum after 1 hour of 5Hz laser deposition, and FIG. 1(d) is the Rhed spectrum after completion of deposition. As can be seen from FIG. 1, at each stage of the deposition of the lead magnesium niobate titanate thin film, lines or points are regularly arranged in the Rhed pattern, which indicates that the lattice arrangement of the thin film is very ordered and is epitaxial growth. In addition, the distance between diffraction lines in the RHEED spectrum is slightly increased, which shows that the lattice parameter is gradually reduced from gallium nitride to lead magnesium niobate titanate, and the buffer layer plays a transition role in the transition. However, since the lattice mismatch is large but within 5%, the buffer layer changes slightly. FIG. 2 is an XRD spectrum of a lead magnesium niobate titanate thin film, from which diffraction peaks in PMN-PT (111) and (222) directions can be clearly seen, and no impurity peak exists, and the surface thin film is oriented and grown along the < 111 > direction. However, since the lattice mismatch is also large but within 5%, the buffer layer variation is also very small, and it is believed that the buffer layer film orientation is consistent with the deposited film itself at 5Hz, which is also the < 111 > direction. The thickness of the lead magnesium niobate titanate thin film in this example was 190 nm.
Example 2
(1) 0.65Pb (Mg) according to chemical composition1/3Nb2/3)O3-0.35PbTiO3Firing the niobium-magnesium-lead titanate ceramic target material by using the mixed powder, wherein the lead dosage is 10% higher than the stoichiometric dosage;
(2) heating the gallium nitride substrate with the orientation of (0002) to 700 ℃, introducing oxygen, and adjusting the oxygen pressure to 6 Pa;
(3) the laser energy is adjusted to 5.5mJ/cm2；
(4) And (3) sputtering deposition process: depositing for 2 minutes by using 1Hz laser, then depositing for 3 minutes by using 2Hz laser, then depositing for 5 minutes by using 3Hz laser, then keeping the 5Hz deposition, stopping for 2 minutes every 10 minutes, and sputtering for 2 hours;
(5) keeping the substrate temperature at 700 ℃ and the oxygen pressure at 6Pa, and annealing in situ for 1 hour. The thickness of the lead magnesium niobate titanate thin film in this example was 198 nm.
Example 3
(1) 0.65Pb (Mg) according to chemical composition1/3Nb2/3)O3-0.35PbTiO3Firing the niobium-magnesium-lead titanate ceramic target material by using the mixed powder, wherein the lead dosage is 10% higher than the stoichiometric dosage;
(2) heating the gallium nitride substrate with the orientation of (0002) to 850 ℃, introducing oxygen, and adjusting the oxygen pressure to 6 Pa;
(3) the laser energy is adjusted to 5.5mJ/cm2；
(4) And (3) sputtering deposition process: depositing for 2 minutes by using 1Hz laser, then depositing for 3 minutes by using 2Hz laser, then depositing for 5 minutes by using 3Hz laser, then keeping the 5Hz deposition, stopping for 2 minutes every 10 minutes, and sputtering for 2 hours;
(5) keeping the temperature of the substrate at 850 ℃ and the oxygen pressure at 6Pa, and annealing in situ for 1 hour. The thickness of the lead magnesium niobate titanate thin film in this example was 182 nm.
Comparative example 1 (deposition temperature 650 ℃ C., less than 700 ℃ C.)
(1) 0.65Pb (Mg) according to chemical composition1/3Nb2/3)O3-0.35PbTiO3Firing the niobium-magnesium-lead titanate ceramic target material by using the mixed powder, wherein the lead dosage is 10% higher than the stoichiometric dosage;
(2) heating the gallium nitride substrate with the orientation of (0002) to 650 ℃, introducing oxygen, and adjusting the oxygen pressure to 6 Pa;
(3) the laser energy is adjusted to 5.5mJ/cm2；
(4) And (3) sputtering deposition process: depositing for 2 minutes by using 1Hz laser, then depositing for 3 minutes by using 2Hz laser, then depositing for 5 minutes by using 3Hz laser, then keeping the 5Hz deposition, stopping for 2 minutes every 10 minutes, and sputtering for 2 hours;
(5) keeping the substrate temperature at 650 ℃ and the oxygen pressure at 6Pa, and annealing in situ for 1 hour. The thickness of the lead magnesium niobate titanate thin film in this example was 210 nm.
FIG. 3 shows Rhed patterns of samples obtained at two different substrate temperatures, (a) is a comparative example 1(650 ℃), and (b) is a example 3(850 ℃), from which it can be seen that the Rhed pattern of the sample obtained at a substrate temperature of 650 ℃ shows ring-like streaks, while the Rhed pattern of the sample obtained at a substrate temperature of 850 ℃ shows aligned lines and dots, indicating that the 650 ℃ sample is a disoriented polycrystalline state and the 850 ℃ sample is a well-oriented epitaxial film.
Claims (10)
1. The method for epitaxially growing the high-quality lead magnesium niobate titanate film on the gallium nitride substrate is characterized in that the compound chemical formula of the lead magnesium niobate titanate film is (1-x) Pb (Mg)1/3Nb2/3)O3-xPbTiO3Wherein x is more than 0 and less than 1, and the preparation method comprises the following steps:
(1) taking lead magnesium niobate titanate ceramic as a target material, taking a (0002) oriented gallium nitride film as a substrate, controlling the temperature of the substrate to 700-850 ℃, introducing oxygen and adjusting the oxygen pressure to 0.5-10 Pa;
(2) adjusting the laser energy to 2-6 mJ/cm2Firstly, depositing a buffer layer on the (0002) oriented gallium nitride substrate in a mode of increasing the laser frequency in sections, then depositing for 1-3 hours at the laser frequency of 5-10Hz, and then annealing in situ to obtain the lead magnesium niobate titanate film.
2. The method of claim 1, wherein depositing the buffer layer in a manner that increases the laser frequency in stages comprises: firstly, 1Hz laser is used for deposition for 1-5 minutes, then 2Hz laser is used for deposition for 1-5 minutes, and then 3Hz laser is used for deposition for 1-5 minutes.
3. The method of claim 2, wherein depositing the buffer layer in a manner that increases the laser frequency in stages comprises: the deposition was carried out with a 1Hz laser for 2 minutes, then with a 2Hz laser for 3 minutes and then with a 3Hz laser for 5 minutes.
4. The method according to any one of claims 1 to 3, wherein the mixed raw material powder is fired into the niobium magnesium lead titanate ceramic at a standard stoichiometric ratio in which the amount of lead is 10 to 15% higher than that at the standard stoichiometric ratio.
5. The method according to any one of claims 1 to 3, wherein in the step (1), the oxygen gas pressure is 2 to 6 Pa.
6. The method according to any one of claims 1 to 3, wherein in the step (2), the laser energy is 5.5mJ/cm2。
7. The method according to any one of claims 1 to 3, wherein in step (2), the in-situ annealing time is 0.5 to 2 hours.
8. The method of claim 7, wherein in step (2), the in-situ annealing time is 1 hour.
9. A gallium nitride-based lead magnesium niobate titanate thin film prepared according to any one of claims 1 to 8, comprising a (0002) oriented gallium nitride thin film and a (111) oriented lead magnesium niobate titanate thin film.
10. The gallium nitride-based lead magnesium niobate titanate thin film according to claim 9, wherein the thickness of the (111) oriented lead magnesium niobate titanate thin film is 80 to 200 nm.
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| CN101956166A (en) * | 2010-10-13 | 2011-01-26 | 上海师范大学 | Method for preparing plumbum magnesium niobate-plumbum titanate ferroelectric film |
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| CN101956166A (en) * | 2010-10-13 | 2011-01-26 | 上海师范大学 | Method for preparing plumbum magnesium niobate-plumbum titanate ferroelectric film |
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