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CN101892522 A Method for preparing lead-titanate-lead-magnesium niobate JIANGSU ADVANCED

films by pulsed laser deposition assisted by oxygen plasmas INORGANIC MATERIAL
RESEARCH INSTITUTE
Method for preparing lead-titanate-lead-magnesium niobate films by pulsed laser

deposition assisted by oxygen plasmas
CN101892522 A
Current assignees IPC - International classification

J I A N G S U A D V A N C E D I N O R G A N I C M A T E R I A L C23C-014/22* C30B-023/00 C30B-029/22
RESEARCH INSTITUTE* C30B-029/30 C30B-029/32
Inventors
LI XIAOMIN
HE YONG
GAO XIANGDONG
LENG XUE
Priority data including date

2010CN-0241301 2010-07-30
Family
CN101892522 B 2013-07-17 CN101892522 A 2010-11-24
(CN101892522)
The invention provides a method for preparing lead-titanate-
lead-magnesium niobate films by pulsed laser deposition
assisted by oxygen plasmas, which is characterized by
introducing high-activity oxygen plasmas to the process of
preparing lead titanium-magnesium niobate films by pulsed
laser deposition and improving the crystallinity and
topography of the oxygen plasmas, thus obtaining the high-
quality lead titanium-magnesium niobate films. The specific
process is as follows: placing the lead-titanate-lead-
magnesium niobate target and the substrate into a vacuum
chamber; vacuumizing the vacuum chamber and heating
the substrate to certain temperature; then pumping certain
amount of high-purity oxygen and ionizing the oxygen by
using a gas ionization system to apply high pressure to form
the high-activity oxygen plasmas; ensuring the oxygen
plasmas between the lead-titanate-lead-magnesium niobate
target and the substrate; and using the high energy pulse
laser to bombard the lead-titanate-lead-magnesium niobate
target to generate the high energy plasmas and depositing
the lead-titanate-lead-magnesium niobate films on the
substrate. The films prepared by the invention have good
crystallization quality, compact structure and excellent
dielectric and ferroelectric properties.
Abstract
(CN101892522)
The invention provides a method for preparing lead-titanate-lead-magnesium niobate films by pulsed laser deposition
assisted by oxygen plasmas, which is characterized by introducing high-activity oxygen plasmas to the process of
preparing lead titanium-magnesium niobate films by pulsed laser deposition and improving the crystallinity and topography
of the oxygen plasmas, thus obtaining the high-quality lead titanium-magnesium niobate films. The specific process is as
follows: placing the lead-titanate-lead-magnesium niobate target and the substrate into a vacuum chamber; vacuumizing
the vacuum chamber and heating the substrate to certain temperature; then pumping certain amount of high-purity oxygen
and ionizing the oxygen by using a gas ionization system to apply high pressure to form the high-activity oxygen plasmas;
ensuring the oxygen plasmas between the lead-titanate-lead-magnesium niobate target and the substrate; and using the
high energy pulse laser to bombard the lead-titanate-lead-magnesium niobate target to generate the high energy plasmas
and depositing the lead-titanate-lead-magnesium niobate films on the substrate. The films prepared by the invention have
good crystallization quality, compact structure and excellent dielectric and ferroelectric properties.
Claims
(CN101892522)
1. A method for preparing lead magnesium titanate niobate thin film by oxygen plasma auxiliary pulse laser deposition
method, firstly, placing lead magnesium titanate target material and substrate in a vacuum chamber, heating the substrate
to a certain temperature after vacuumizing, characterized in that high purity oxygen is introduced into the vacuum chamber
and high pressure is applied by an external power supply to plasmize the oxygen, then the target material is bombarded by
high energy pulse laser, high energy plasma is generated by evaporation on the surface layer of the target material, and
the high energy plasma is transmitted to the substrate to deposit and form film.
2. The method of claim 1, characterized by the specific steps of:
a, preparing a target material: adopting lead magnesium niobate titanate (1-x) Pb (Mg)1/3Nb2/3)O3-xPbTiO3Ceramic or
single crystal target material, PbTiO of target material3The mole percentage is more than 0 percent to 40 percent; firstly,
polishing a target material to level the surface, then putting the target material into a mixed solution of ethanol and
deionized water for ultrasonic cleaning, drying and then putting the target material into a vacuum chamber;
b, substrate preparation: adopting a silicon substrate or a single crystal substrate with a bottom electrode film, wherein the
bottom electrode film on the substrate is a metal or metal oxide film, then putting the substrate into a mixed solution of
ethanol and deionized water for ultrasonic cleaning, washing the surface with the deionized water, drying the surface with
nitrogen, and putting the substrate into a vacuum chamber;
c, depositing the lead magnesium niobate titanate film by an oxygen plasma assisted pulse laser method: putting the lead
magnesium niobate titanate target material obtained in the step a and the substrate treated in the step b into a vacuum
chamber, and pumping the vacuum chamber to a vacuum degree higher than 3 multiplied by 10-4Heating the substrate to
400-;
d, preparing a top electrode: and (3) placing mask plates with different hole diameters on the lead magnesium niobate
titanate thin film, depositing a metal or metal oxide top electrode thin film, and finally preparing a sandwich thin film
structure consisting of a bottom electrode, the lead magnesium niobate titanate thin film and a top electrode.
3. The method of claim 2, wherein the gas ionization system is located between the target and the substrate.
4. The method of claim 2, wherein said silicon substrate is Si (100) or Si (111);the single crystal substrate is Mg (100) or
LaAlO3。
5. The method of claim 2, wherein the bottom electrode metal or metal oxide film of the substrate in step b is Pt, Ir, LaxSr1-
xCoO3Or SrRuO3。
6. The method of claim 2 wherein in step c the gas ionization system applies a high voltage of 400V to plasmatize the
oxygen at a current of 400A.
7. The method of claim 2 wherein said laser of step c has a laser power of 5J/cm2The pulse frequency was 5Hz, and the
distance between the target and the substrate was 10 cm.
8. The method of claim 2, wherein the top electrode is Pt, Ir, LaxSr1-xCoO3Or SrRuO3A film.
9. The method according to claim 1 or 2, wherein the magnesium niobate titanate thin film produced has a perovskite
structure with a (100) plane height-preferred orientation.
10. A process according to claim 1 or 2, characterised in that the composition is 0.85Pb (Mg)1/3Nb2/3)O3-0.15PbTiO3The
film has a dielectric constant of 3258 at 1KHz frequency, a dielectric loss of 0.7%, and a small change in dielectric constant
over a wide frequency range.
Description
(CN101892522)
TECHNICAL FIELD
The invention relates to a method for preparing a lead magnesium titanate niobate titanate film by using oxygen plasma
and pulse laser deposition technology, belonging to the technical field of electronic materials.
BACKGROUND ART
Lead magnesium niobate titanate thin films have great application prospects in the fields of thin film capacitors, nonvolatile
ferroelectric memories, actuators, sensors, electro-optical devices, detectors, and the like due to their excellent dielectric,
ferroelectric, piezoelectric, electro-optical, and pyroelectric properties [ Park et al, Journal of Applied physics.82,
1804(1997), Zhao et al, Materials Science and Engineering B-Solid State Materials for Advanced technology.96, 254(2002)
].
Lead magnesium titano-niobate films are highly susceptible to oxygen deficiency during fabrication to form impurity phases
and to generate oxygen vacancies and other related defects, resulting in excessive leakage current and deterioration of
dielectric and ferroelectric properties, and therefore typically require fabrication in an atmosphere with high oxygen partial
pressure [ Tantigate et al, Applied Physics letters.66, 1611(1995) ]. However, for most vacuum sputtering deposition
methods, such as a pulsed laser deposition method and a radio frequency magnetron sputtering method, the high oxygen
pressure condition easily causes the collision between the film forming ions and oxygen molecules in the atmosphere
before reaching the substrate in the deposition process, so as to reduce the energy of the film forming ions, and
simultaneously, the increase of the oxygen partial pressure reduces the mean free path of the film forming particles
adsorbed on the substrate, and reduces the atomic diffusion probability between crystal grains, so that the contact
compactness between the crystal grains is reduced, the crystal boundary structure is loose, and thus various performances
of the lead magnesium titanate niobate titanate thin film are deteriorated. Therefore, the method for preparing the lead
magnesium titanate niobate thin film with the highly preferred orientation perovskite structure solves the problem of oxygen
deficiency of the lead magnesium titanate niobate thin film, and has good crystallization quality and compact structure, so
that the thin film has excellent dielectric and ferroelectric properties, and is a difficult problem to be solved urgently in the
preparation of the lead magnesium titanate niobate thin film by the existing pulse laser deposition method.
DISCLOSURE
Disclosure of Invention
The invention aims to provide a method for preparing a lead magnesium titanate niobate thin film with high preferred
orientation, high crystallization quality and compact structure by adopting an oxygen plasma assisted pulse laser deposition
technology. The method is also applicable to other ferroelectric oxide thin films.
The invention provides a method for preparing a lead magnesium titanate niobate thin film by using an oxygen plasma
assisted pulse laser deposition method, which comprises the following steps in sequence:
step 1: and (4) preparing a target material. Adopting lead magnesium niobate titanate (1-x) Pb (Mg)1/3Nb2/3)O3-
xPbTiO3Ceramic or single crystal target material, PbTiO of target material3The mole percentage is more than 0 percent to
40 percent. Polishing the target material to level the surface, then putting the target material into mixed solution of ethanol
and deionized water for ultrasonic cleaning, drying and then putting the target material into a vacuum chamber.
Step 2: a substrate is prepared. Using a silicon substrate or single crystal substrate with a bottom electrode film, e.g. Si
(100), Si (111), MgO (100), LaAlO3And the like. The bottom electrode film on the substrate is a metal or metal oxide film,
such as Pt, Ir, LaxSr1-xCoO3、SrRuO3And the like. Then putting the substrate into mixed solution of ethanol and
deionized water for ultrasonic cleaning, washing the surface with deionized water, drying by using nitrogen, and putting into
a vacuum chamber.
And step 3: and depositing the lead magnesium niobate titanate film by an oxygen plasma assisted pulse laser method.
Putting the lead magnesium niobate titanate target prepared in the step 1 and the substrate processed in the step 2 into a
vacuum chamber, and pumping the vacuum chamber to a vacuum degree higher than 3 multiplied by 10-4Heating the
substrate to 400-800 ℃ after Pa, introducing high-purity oxygen with oxygen partial pressure of 1-20Pa in the process of
depositing the lead magnesium niobate titanate film, and applying 100-50 Pa by a gas ionization systemThe oxygen is
plasmatized under the high pressure of 0V, the gas ionization system is positioned between the target material and the
substrate, the laser generated by the excimer laser is guided into the vacuum chamber through the optical guide-in system
to bombard the lead magnesium titanate ceramic target material, the plasma is evaporated to interact with the oxygen
plasma, and then the plasma is transmitted to the substrate to be deposited into the lead magnesium titanate film.
And 4, step 4: and preparing a top electrode. Placing masks with different hole diameters on the lead magnesium niobate
titanate film, and depositing a metal or metal oxide top electrode film, wherein the top electrode film is a metal or metal
oxide film, such as Pt, Ir, LaxSr1-xCoO3、SrRuO3And the like. Finally, a sandwich film structure consisting of a bottom
electrode, a lead magnesium niobate titanate film and a top electrode is manufactured.
In summary, the invention firstly puts the lead magnesium niobate titanate target material and the substrate in a vacuum
chamber, heats the substrate to a certain temperature after vacuumizing, and is characterized in that high-purity oxygen is
introduced into the vacuum chamber, high voltage is applied by an external power supply to plasmize the oxygen, then the
target material is bombarded by high-energy pulse laser, high-energy plasma is generated on the surface layer of the target
material by evaporation, and the high-energy plasma is transmitted to the substrate to deposit and form a film.
The invention is characterized in that the ferroelectric film with compact structure and excellent performance which can be
used in a plurality of fields such as film capacitors, nonvolatile ferroelectric memories, actuators, sensors, electro-optical
devices, detectors and the like is obtained by assisting high-efficiency oxygen supplementation by oxygen plasmas and
optimizing the film deposition growth conditions.
At present, most of the titanium lead magnesium niobate thin films prepared under the condition of high oxygen partial
pressure have loose structures, and the dielectric constant at room temperature is between 200-2000 [ Donnelly et al,
Journal of Applied Physics.93, 9924(2003) ]. The invention introduces high-activity oxygen ions in the preparation process
of the lead magnesium niobate titanate film, and obtains the lead magnesium niobate titanate film which has a compact
structure and a dielectric constant close to a block material (Chen et al, Materials letters.57, 20 (2002)) under the condition
of low oxygen partial pressure.
DRAWINGS DESCRIPTION
FIG. 1 is an X-ray diffraction pattern of the lead magnesium niobate titanate thin film prepared in example 1.
FIG. 2 is a scanning electron micrograph (a) of the surface (b) of the lead magnesium niobate titanate thin film prepared in
example 1.
FIG. 3 shows the dielectric spectrum of the lead magnesium titanozoaniobate thin film prepared in example 1.
FIG. 4 is a hysteresis loop of the lead magnesium titanyl niobate thin film prepared in example 1.
INVENTION MODE
Detailed Description
Example 1
In the embodiment, the lead magnesium niobate titanate thin film is prepared by adopting a plasma assisted pulse laser
deposition method, and the specific process steps are as follows:
a) preparing a target material: 0.67Pb (Mg) was selected1/3Nb2/3)O3-0.33PbTiO3Polishing the target material to level the
surface, then putting the target material into mixed solution of ethanol and deionized water for ultrasonic cleaning, drying
and putting the target material into a vacuum chamber.
b) Substrate preparation: ultrasonic cleaning epitaxial Ir/SrTiO with ethanol and deionized water mixed solution3the/Si
(100) substrate was rinsed with deionized water and then blown dry with nitrogen into a vacuum chamber. Vacuumizing to
more than 3X 10-4Pa, and heating the substrate to a temperature of 650 ℃.
c) Preparing a lead magnesium titanate niobate thin film: high-purity oxygen is filled into the vacuum chamber, the oxygen
partial pressure is adjusted to be 2Pa, the oxygen is plasmatized by applying 400V high pressure through a gas ionization
system, the current is 40mA, and the oxygen plasma is positioned between the target material and the substrate. Adjusting
the laser to guide the laser beam into the vacuum chamber through the optical system, focusing on the lead magnesium
titanate niobate ceramic target to generate a plume of the lead magnesium titanate material, and transmitting the plume to
the substrate for deposition and growth through the interaction of the oxygen plasma and the plumeAnd obtaining the lead
magnesium niobate titanate film. The laser energy adopted is 5J/cm2The pulse frequency was 5Hz, and the target-
substrate spacing was 10 cm. The equipment used for preparing the lead magnesium niobate titanate film is PLD450 type
pulse laser coating equipment of Shenyang scientific instrument development center limited company of Chinese academy
of sciences and a gas ionization system thereof.
d) Preparing a top electrode: a mask plate with the hole diameter of 0.5mm is arranged on the lead magnesium niobate
titanate thin film; by electron beam evaporation using high purity Ti target at 1X 10-3Depositing Ti with the thickness of 5nm
under the Pa vacuum condition; using a high purity Pt target at 1X 10-3Pt electrodes with a thickness of 50nm were
deposited under Pa vacuum. The bottom electrode Ir, the lead magnesium niobate titanate film and the top electrode Pt
form a sandwich structure.
X-ray diffraction (XRD) analysis shows that the lead magnesium niobate titanate thin film prepared by the method is a
perovskite structure with (100) plane height preferred orientation and has good crystallization quality (see figure 1). As
shown in the scanning electron microscope topography of FIG. 2, the film showed a dense structure. FIG. 3 is a dielectric
spectrum of a lead magnesium titanozoaniobate thin film. It can be seen from the figure that there are high dielectric
constants and low dielectric losses over a large frequency range. The dielectric constant at 1KHz frequency was 3258 and
the dielectric loss was 0.7%. The dielectric constant does not change much over a wide frequency range and drops rapidly
above 100kHz, while the dielectric loss increases rapidly. FIG. 4 is a ferroelectric hysteresis loop of a PMN-PT film having a
remanent polarization of 19 μ C/cm2Coercive force of 35kV/cm and saturation polarization of 80 mu C/cm2。
Example 2
a) preparing a target material: 0.85Pb (Mg) is selected1/3Nb2/3)O3-0.15PbTiO3The film takes single crystal as a target
material, and is put into a vacuum chamber after being cleaned and dried.
b) Substrate preparation: mixing with ethanol and deionized waterUltrasonic cleaning La-plated composite
solution0.5Sr0.5CoO3The MgO single crystal substrate of the oxide film electrode is washed with deionized water on the
surface, dried with nitrogen and placed in a vacuum chamber. Vacuumizing until the back bottom vacuum is 3 multiplied by
10-4Pa, and heating the substrate to a temperature of 600 ℃.
c) Preparing a lead magnesium titanate niobate thin film: and (3) filling high-purity oxygen into the vacuum chamber,
adjusting the oxygen partial pressure to be 5Pa, applying high voltage through a gas ionization system to enable the
oxygen to be ionized into plasma, wherein the applied voltage is 300V, the current is 30mA, and the oxygen plasma is
positioned between the target material and the substrate. And adjusting a laser to lead a laser beam into the vacuum
chamber through an optical system, focusing the laser beam on the lead magnesium titanate niobate ceramic target to
generate a plume of the lead magnesium titanate niobate material, and transmitting the plume of the lead magnesium
titanate material to a substrate for deposition and growth through interaction of oxygen plasma. The laser energy adopted
is 5J/cm2The pulse frequency was 3Hz, and the target-substrate spacing was 10 cm. The equipment used for preparing
the lead magnesium niobate titanate film is PLD450 type pulse laser coating equipment of Shenyang scientific instrument
development center limited company of Chinese academy of sciences and a gas ionization system thereof.
deposited under Pa vacuum. Bottom electrode La0.5Sr0.5CoO3The lead magnesium niobate titanate thin film and the top
electrode Pt form a sandwich structure.
The XRD, current profile, dielectric spectrum, hysteresis loop and the like of the lead magnesium niobate prepared in the
embodiment are the same as those of the figures 1 to 4 shown in the embodiment 1.
(CN101892522)
技术领域
本发明涉及一种利用氧等离子体和脉冲激光沉积技术制备钛铌镁酸铅薄膜的方法, 属于电子材料技术领域。
背景技术
钛铌镁酸铅薄膜由于其优异的介电、铁电、压电、电光和热释电性能, 因此在薄膜电容器、非易失铁电存储器、致动器、传
感器、电光器件和探测器等领域有巨大的应用前景[ Park 等, Journal of Applied Physics . 82,1804 ( 1997 ) 和Zhao 等,
Materials Science and Engineering B - Solid State Materials for Advanced Technology . 96,254 ( 2002 ) ] 。
钛铌镁酸铅薄膜在制备过程极易缺氧而形成杂质相并产生氧空位等相关缺陷, 从而导致漏电流过大、介电和铁电等性能恶化,
因此通常需要在高氧分压气氛中制备[ Tantigate 等, Applied Physics Letters . 66,1611 ( 1995 ) ] 。然而对于大多真空溅射沉
积方法, 如脉冲激光沉积方法、射频磁控溅射方法, 高氧压条件容易引起沉积过程中成膜离子在达到衬底之前和气氛中的氧分
子发生碰撞, 降低成膜离子的能量, 同时, 氧分压升高降低了吸附于衬底上的成膜粒子的平均自由程, 降低了晶粒与晶粒之间的
原子扩散几率, 致使晶粒之间接触的致密性下降, 晶界结构松散, 从而使钛铌镁酸铅薄膜的各种性能恶化。因此, 制备高度择优
取向的钙钛矿结构钛铌镁酸铅薄膜, 并在解决钛铌镁酸铅薄膜缺氧问题的同时结晶质量良好、结构致密, 从而使薄膜具有优异
介电、铁电等性能, 是目前脉冲激光沉积方法制备钛铌镁酸铅薄膜急需解决的难题。
发明内容
本发明的目的在于, 提供一种采用氧等离子辅助的脉冲激光沉积技术制备高度择优取向、结晶质量高、结构致密的钛铌镁酸
铅薄膜的方法, 本发明旨在通过在脉冲激光沉积过程中引入高化学活性的氧等离子体, 在较低氧分压的条件实现高效补氧, 同
时减少成膜离子与氧离子碰撞, 得到介电、铁电性能优异的钛铌镁酸铅薄膜。该方法还适用于其他铁电氧化物薄膜。
本发明提供的利用氧等离子体辅助脉冲激光沉积法制备钛铌镁酸铅薄膜的方法, 包括以下顺序步骤:
步骤1 : 靶材准备。采用钛铌镁酸铅( 1- x ) Pb ( Mg 1/3 Nb 2/3 ) O 3 -
xPbTiO 3 陶瓷或单晶靶材靶材, 靶材的PbTiO 3 摩尔百分比在大于0% ～40% 之间。将靶
材通过打磨平整表面, 然后放入乙醇和去离子水混合溶液中超声清洗, 烘干后置入真空室。
步骤2 : 衬底准备。采用带底电极薄膜地硅衬底或单晶衬底, 如Si ( 100 ) 、Si ( 111 ) 、MgO ( 100 ) 、LaAlO 3 等。衬底上的底电极薄膜为金属或金属氧化物薄膜, 如Pt 、Ir 、La x Sr 1- x CoO 3 、SrRuO 3 等。然后将衬底放入乙醇和去离子水的混合溶液中超声清洗, 再用去离子水冲
洗表面, 并用氮气吹干后置入真空室。
步骤3 : 氧等离子体辅助脉冲激光方法沉积钛铌镁酸铅薄膜。将步骤1 准备的钛铌镁酸铅靶材和步骤2 处理后的衬底置入真空
室中, 在将真空度抽至高于3 ×10 - 4 Pa 后把衬底加热至400-800 ℃温度, 在沉积钛铌镁酸铅薄膜过程中通
入1-20 Pa 氧分压的高纯氧气, 并通过气体电离系统施加100-500 V 高压使氧气等离子化, 气体电离系统位于靶材和衬底之间,
通过光学导入系统将准分子激光器产生的激光导入真空室轰击钛铌镁酸铅陶瓷靶材, 蒸发出等离子体与氧等离子体相互作用,
然后传输到衬底上沉积成钛铌镁酸铅薄膜。
步骤4 : 顶电极制备。将不同孔洞直径的掩膜板置于钛铌镁酸铅薄膜之上, 沉积金属或金属氧化物顶电极薄膜, 顶电极薄膜为
金属或金属氧化物薄膜, 如Pt 、Ir 、La x Sr 1- x CoO 3 、SrRuO 3 等。最终制成由底电极、钛铌镁酸铅薄膜和顶电极组成的三明治薄膜结构。
总之, 本发明首先将钛铌镁酸铅靶材和衬底置于真空室中, 抽真空后将衬底加热到一定温度, 其特征在于接着向真空室通入高
纯氧气并用外部电源施加高压将氧气等离子化, 然后通过高能脉冲激光轰击靶材, 在靶材表层蒸发产生高能等离子体, 传输到
衬底上沉积成膜。
本发明的特点是, 通过氧等离子体辅助高效补氧、优化薄膜沉积生长条件, 获得可用于薄膜电容器、非易失铁电存储器、致动
器、传感器、电光器件和探测器等多个领域的结构致密、性能优异的铁电薄膜。
目前, 在采用高氧分压条件制备钛铌镁酸铅薄膜大多结构松散, 室温介电常数在200-2000 之间[ Donnelly 等, Journal of
Applied Physics . 93,9924 ( 2003 ) ] 。本发明通过在钛铌镁酸铅薄膜制备过程中引入高活性的氧离子, 在低氧分压条件下得
到结构致密, 介电常数接近块体材料[ Chen 等, Materials Letters . 57,20 ( 2002 ) ] 的钛铌镁酸铅薄膜。
附图说明
图1 为实施例1 制备的钛铌镁酸铅薄膜X 射线衍射图谱。
图2 为实施例1 制备的钛铌镁酸铅薄膜扫描电镜形貌图( a ) 表面( b ) 截面。
图3 为实施例1 制备的钛铌镁酸铅薄膜介电频谱。
图4 为实施例1 制备的钛铌镁酸铅薄膜电滞回线。
具体实施方式
实施例1
本实例中, 钛铌镁酸铅薄膜采用等氧离子体辅助脉冲激光沉积法制备, 具体工艺步骤如下:
a ) 靶材准备: 选择0.67 Pb ( Mg 1/3 Nb 2/3 ) O 3 - 0.33 PbTiO 
3 陶瓷作为靶材, 将靶材通过打磨平整表面, 然后放入乙醇和去离子水混合溶液中超声清洗, 烘干后置入真空室。
b ) 衬底准备: 用乙醇和去离子水混合溶液超声清洗外延Ir / SrTiO 3 / Si ( 100 ) 衬底, 用去离子水冲洗表面,
然后用氮气吹干放入真空室中。抽真空至高于3 ×10 - 4 Pa , 加热衬底至温度650 ℃。
c ) 钛铌镁酸铅薄膜制备: 向真空室充入高纯氧气, 调整氧分压为2 Pa , 通过气体电离系统施加400 V 高压使氧气等离子化, 电
流为40 mA , 氧等离子体位于靶材和衬底之间。调整激光器使激光束经过光学系统导入真空室, 聚焦在钛铌镁酸铅陶瓷靶材上,
产生钛铌镁酸铅材料羽辉, 经过氧等离子体与之相互作用, 传输至衬底上沉积生长得钛铌镁酸铅薄膜。所采用的激光能量为5 J
/ cm 2 , 脉冲频率为5 Hz , 靶材- 衬底间距为10 cm 。制备钛铌镁酸铅薄膜所采用的设备为中国科学院沈阳
科学仪器研制中心有限公司的PLD450 型脉冲激光镀膜设备及其气体电离系统。
d ) 顶电极制备: 采用孔洞直径为0.5 mm 的掩膜板置于钛铌镁酸铅薄膜之上; 采用电子束蒸发法, 使用高纯Ti 靶, 在1 ×10 - 3 Pa 真空条件下沉积厚度为5 nm 的Ti ; 使用高纯Pt 靶, 在1 ×10 - 3 Pa 真空条件下沉积厚
度为50 nm 的Pt 电极。底电极Ir 、钛铌镁酸铅薄膜和顶电极Pt 形成三明治结构。
X 射线衍射( XRD ) 分析表明, 上述方法制备的钛铌镁酸铅薄膜为( 100 ) 面高度择优取向的钙钛矿型结构, 结晶质量良好( 参见
附图1 ) 。由附图2 扫描电镜形貌图所示, 薄膜呈现致密的结构。附图3 是钛铌镁酸铅薄膜介电频谱。从图可以看出, 在较大频
率范围内具有高介电常数和低介电损耗。在1 KHz 频率处介电常数为3258, 介电损耗为0.7% 。介电常数在很大的频率范围下
变化不大, 在高于100 kHz 后迅速下降, 与此同时介电损耗迅速增大。附图4 为PMN - PT 薄膜的电滞回线, 其剩余极化强度为
19 μC / cm 2 , 矫顽力为35 kV / cm , 饱和极化强度为80 μC / cm 2 。
实施例2
本实例中, 钛铌镁酸铅薄膜采用等氧离子体辅助脉冲激光沉积法制备, 具体工艺步骤如下:
a ) 靶材准备: 选择0.85 Pb ( Mg 1/3 Nb 2/3 ) O 3 - 0.15 PbTiO 
3 薄膜以单晶作为靶材, 清洗烘干后放入真空室中。
b ) 衬底准备: 用乙醇和去离子水混合溶液超声清洗镀有La 0.5 Sr 0.5 CoO 3 氧化物薄膜电极的MgO 单晶衬底, 用去离子水冲洗表面, 然后用氮气吹干放入真空室中。抽真空至背底真空为3 ×10 - 4 Pa , 加热衬底至温度600 ℃。
c ) 钛铌镁酸铅薄膜制备: 向真空室充入高纯氧气, 调整氧分压为5 Pa , 通过气体电离系统施加高压使氧气等离子化, 所施加电
压为300 V , 电流为30 mA , 氧等离子体位于靶材和衬底之间。调整激光器使激光束经过光学系统导入真空室, 聚焦在钛铌镁
酸铅陶瓷靶材上, 产生钛铌镁酸铅材料羽辉, 经过氧等离子体与之相互作用, 传输至衬底上沉积生长得钛铌镁酸铅薄膜。所采
用的激光能量为5 J / cm 2 , 脉冲频率为3 Hz , 靶材- 衬底间距为10 cm 。制备钛铌镁酸铅薄膜所采用的设备
为中国科学院沈阳科学仪器研制中心有限公司的PLD450 型脉冲激光镀膜设备及其气体电离系统。
d ) 顶电极制备: 采用孔洞直径为0.5 mm 的掩膜板置于钛铌镁酸铅薄膜之上; 采用电子束蒸发法, 使用高纯Ti 靶, 在1 ×10 - 3 Pa 真空条件下沉积厚度为5 nm 的Ti ; 采用高纯Pt 靶, 在1 ×10 - 3 Pa 真空条件下沉积厚
度为50 nm 的Pt 电极。底电极La 0.5 Sr 0.5 CoO 3 、钛铌镁酸铅薄膜
和顶电极Pt 形成三明治结构。
本实施例所制成的铌镁酸铅的XRD 、电流形貌图以及介电频谱、电滞回线等均与实施例1 所示的图1- 图4 雷同。
English description
(CN101892522)
TECHNICAL FIELD
The invention relates to a method for preparing a lead magnesium titanate niobate titanate film by using oxygen plasma
and pulse laser deposition technology, belonging to the technical field of electronic materials.
BACKGROUND ART
Lead magnesium niobate titanate thin films have great application prospects in the fields of thin film capacitors, nonvolatile
ferroelectric memories, actuators, sensors, electro-optical devices, detectors, and the like due to their excellent dielectric,
ferroelectric, piezoelectric, electro-optical, and pyroelectric properties [ Park et al, Journal of Applied physics.82,
1804(1997), Zhao et al, Materials Science and Engineering B-Solid State Materials for Advanced technology.96, 254(2002)
].
Lead magnesium titano-niobate films are highly susceptible to oxygen deficiency during fabrication to form impurity phases
and to generate oxygen vacancies and other related defects, resulting in excessive leakage current and deterioration of
dielectric and ferroelectric properties, and therefore typically require fabrication in an atmosphere with high oxygen partial
pressure [ Tantigate et al, Applied Physics letters.66, 1611(1995) ]. However, for most vacuum sputtering deposition
methods, such as a pulsed laser deposition method and a radio frequency magnetron sputtering method, the high oxygen
pressure condition easily causes the collision between the film forming ions and oxygen molecules in the atmosphere
before reaching the substrate in the deposition process, so as to reduce the energy of the film forming ions, and
simultaneously, the increase of the oxygen partial pressure reduces the mean free path of the film forming particles
adsorbed on the substrate, and reduces the atomic diffusion probability between crystal grains, so that the contact
compactness between the crystal grains is reduced, the crystal boundary structure is loose, and thus various performances
of the lead magnesium titanate niobate titanate thin film are deteriorated. Therefore, the method for preparing the lead
magnesium titanate niobate thin film with the highly preferred orientation perovskite structure solves the problem of oxygen
deficiency of the lead magnesium titanate niobate thin film, and has good crystallization quality and compact structure, so
that the thin film has excellent dielectric and ferroelectric properties, and is a difficult problem to be solved urgently in the
preparation of the lead magnesium titanate niobate thin film by the existing pulse laser deposition method.
DISCLOSURE
Disclosure of Invention
The invention aims to provide a method for preparing a lead magnesium titanate niobate thin film with high preferred
orientation, high crystallization quality and compact structure by adopting an oxygen plasma assisted pulse laser deposition
technology. The method is also applicable to other ferroelectric oxide thin films.
The invention provides a method for preparing a lead magnesium titanate niobate thin film by using an oxygen plasma
assisted pulse laser deposition method, which comprises the following steps in sequence:
step 1: and (4) preparing a target material. Adopting lead magnesium niobate titanate (1-x) Pb (Mg)1/3Nb2/3)O3-
xPbTiO3Ceramic or single crystal target material, PbTiO of target material3The mole percentage is more than 0 percent to
40 percent. Polishing the target material to level the surface, then putting the target material into mixed solution of ethanol
and deionized water for ultrasonic cleaning, drying and then putting the target material into a vacuum chamber.
Step 2: a substrate is prepared. Using a silicon substrate or single crystal substrate with a bottom electrode film, e.g. Si
(100), Si (111), MgO (100), LaAlO3And the like. The bottom electrode film on the substrate is a metal or metal oxide film,
such as Pt, Ir, LaxSr1-xCoO3、SrRuO3And the like. Then putting the substrate into mixed solution of ethanol and
deionized water for ultrasonic cleaning, washing the surface with deionized water, drying by using nitrogen, and putting into
a vacuum chamber.
And step 3: and depositing the lead magnesium niobate titanate film by an oxygen plasma assisted pulse laser method.
Putting the lead magnesium niobate titanate target prepared in the step 1 and the substrate processed in the step 2 into a
vacuum chamber, and pumping the vacuum chamber to a vacuum degree higher than 3 multiplied by 10-4Heating the
substrate to 400-800 ℃ after Pa, introducing high-purity oxygen with oxygen partial pressure of 1-20Pa in the process of
depositing the lead magnesium niobate titanate film, and applying 100-50 Pa by a gas ionization systemThe oxygen is
plasmatized under the high pressure of 0V, the gas ionization system is positioned between the target material and the
substrate, the laser generated by the excimer laser is guided into the vacuum chamber through the optical guide-in system
to bombard the lead magnesium titanate ceramic target material, the plasma is evaporated to interact with the oxygen
plasma, and then the plasma is transmitted to the substrate to be deposited into the lead magnesium titanate film.
And 4, step 4: and preparing a top electrode. Placing masks with different hole diameters on the lead magnesium niobate
titanate film, and depositing a metal or metal oxide top electrode film, wherein the top electrode film is a metal or metal
oxide film, such as Pt, Ir, LaxSr1-xCoO3、SrRuO3And the like. Finally, a sandwich film structure consisting of a bottom
electrode, a lead magnesium niobate titanate film and a top electrode is manufactured.
In summary, the invention firstly puts the lead magnesium niobate titanate target material and the substrate in a vacuum
chamber, heats the substrate to a certain temperature after vacuumizing, and is characterized in that high-purity oxygen is
introduced into the vacuum chamber, high voltage is applied by an external power supply to plasmize the oxygen, then the
target material is bombarded by high-energy pulse laser, high-energy plasma is generated on the surface layer of the target
material by evaporation, and the high-energy plasma is transmitted to the substrate to deposit and form a film.
The invention is characterized in that the ferroelectric film with compact structure and excellent performance which can be
used in a plurality of fields such as film capacitors, nonvolatile ferroelectric memories, actuators, sensors, electro-optical
devices, detectors and the like is obtained by assisting high-efficiency oxygen supplementation by oxygen plasmas and
optimizing the film deposition growth conditions.
At present, most of the titanium lead magnesium niobate thin films prepared under the condition of high oxygen partial
pressure have loose structures, and the dielectric constant at room temperature is between 200-2000 [ Donnelly et al,
Journal of Applied Physics.93, 9924(2003) ]. The invention introduces high-activity oxygen ions in the preparation process
of the lead magnesium niobate titanate film, and obtains the lead magnesium niobate titanate film which has a compact
structure and a dielectric constant close to a block material (Chen et al, Materials letters.57, 20 (2002)) under the condition
of low oxygen partial pressure.
DRAWINGS DESCRIPTION
FIG. 1 is an X-ray diffraction pattern of the lead magnesium niobate titanate thin film prepared in example 1.
FIG. 2 is a scanning electron micrograph (a) of the surface (b) of the lead magnesium niobate titanate thin film prepared in
example 1.
FIG. 3 shows the dielectric spectrum of the lead magnesium titanozoaniobate thin film prepared in example 1.
FIG. 4 is a hysteresis loop of the lead magnesium titanyl niobate thin film prepared in example 1.
INVENTION MODE
Detailed Description
Example 1
a) preparing a target material: 0.67Pb (Mg) was selected1/3Nb2/3)O3-0.33PbTiO3Polishing the target material to level the
surface, then putting the target material into mixed solution of ethanol and deionized water for ultrasonic cleaning, drying
and putting the target material into a vacuum chamber.
b) Substrate preparation: ultrasonic cleaning epitaxial Ir/SrTiO with ethanol and deionized water mixed solution3the/Si
(100) substrate was rinsed with deionized water and then blown dry with nitrogen into a vacuum chamber. Vacuumizing to
more than 3X 10-4Pa, and heating the substrate to a temperature of 650 ℃.
c) Preparing a lead magnesium titanate niobate thin film: high-purity oxygen is filled into the vacuum chamber, the oxygen
partial pressure is adjusted to be 2Pa, the oxygen is plasmatized by applying 400V high pressure through a gas ionization
system, the current is 40mA, and the oxygen plasma is positioned between the target material and the substrate. Adjusting
the laser to guide the laser beam into the vacuum chamber through the optical system, focusing on the lead magnesium
titanate niobate ceramic target to generate a plume of the lead magnesium titanate material, and transmitting the plume to
the substrate for deposition and growth through the interaction of the oxygen plasma and the plumeAnd obtaining the lead
magnesium niobate titanate film. The laser energy adopted is 5J/cm2The pulse frequency was 5Hz, and the target-
substrate spacing was 10 cm. The equipment used for preparing the lead magnesium niobate titanate film is PLD450 type
pulse laser coating equipment of Shenyang scientific instrument development center limited company of Chinese academy
of sciences and a gas ionization system thereof.
deposited under Pa vacuum. The bottom electrode Ir, the lead magnesium niobate titanate film and the top electrode Pt
form a sandwich structure.
X-ray diffraction (XRD) analysis shows that the lead magnesium niobate titanate thin film prepared by the method is a
perovskite structure with (100) plane height preferred orientation and has good crystallization quality (see figure 1). As
shown in the scanning electron microscope topography of FIG. 2, the film showed a dense structure. FIG. 3 is a dielectric
spectrum of a lead magnesium titanozoaniobate thin film. It can be seen from the figure that there are high dielectric
constants and low dielectric losses over a large frequency range. The dielectric constant at 1KHz frequency was 3258 and
the dielectric loss was 0.7%. The dielectric constant does not change much over a wide frequency range and drops rapidly
above 100kHz, while the dielectric loss increases rapidly. FIG. 4 is a ferroelectric hysteresis loop of a PMN-PT film having a
remanent polarization of 19 μ C/cm2Coercive force of 35kV/cm and saturation polarization of 80 mu C/cm2。
Example 2
a) preparing a target material: 0.85Pb (Mg) is selected1/3Nb2/3)O3-0.15PbTiO3The film takes single crystal as a target
material, and is put into a vacuum chamber after being cleaned and dried.
b) Substrate preparation: mixing with ethanol and deionized waterUltrasonic cleaning La-plated composite
solution0.5Sr0.5CoO3The MgO single crystal substrate of the oxide film electrode is washed with deionized water on the
surface, dried with nitrogen and placed in a vacuum chamber. Vacuumizing until the back bottom vacuum is 3 multiplied by
10-4Pa, and heating the substrate to a temperature of 600 ℃.
c) Preparing a lead magnesium titanate niobate thin film: and (3) filling high-purity oxygen into the vacuum chamber,
adjusting the oxygen partial pressure to be 5Pa, applying high voltage through a gas ionization system to enable the
oxygen to be ionized into plasma, wherein the applied voltage is 300V, the current is 30mA, and the oxygen plasma is
positioned between the target material and the substrate. And adjusting a laser to lead a laser beam into the vacuum
chamber through an optical system, focusing the laser beam on the lead magnesium titanate niobate ceramic target to
generate a plume of the lead magnesium titanate niobate material, and transmitting the plume of the lead magnesium
titanate material to a substrate for deposition and growth through interaction of oxygen plasma. The laser energy adopted
is 5J/cm2The pulse frequency was 3Hz, and the target-substrate spacing was 10 cm. The equipment used for preparing
the lead magnesium niobate titanate film is PLD450 type pulse laser coating equipment of Shenyang scientific instrument
development center limited company of Chinese academy of sciences and a gas ionization system thereof.
deposited under Pa vacuum. Bottom electrode La0.5Sr0.5CoO3The lead magnesium niobate titanate thin film and the top
electrode Pt form a sandwich structure.
The XRD, current profile, dielectric spectrum, hysteresis loop and the like of the lead magnesium niobate prepared in the
embodiment are the same as those of the figures 1 to 4 shown in the embodiment 1.
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CN101892522 A Method for preparing lead-titanate-lead-magnesium niobate JIANGSU ADVANCED

Method for preparing lead-titanate-lead-magnesium niobate films by pulsed laser

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