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Publication numbers Title Current assignees
CN105762197 A Lead magnesium niobate and lead titanate monocrystalline- JIANGSU INSTITUTE OF
based semiconductor ferroelectric field effect ADVANCED INORGANIC
heterostructure, manufacture method therefor and MATERIALS
application thereof
Lead magnesium niobate and lead titanate monocrystalline-based semiconductor

ferroelectric field effect heterostructure, manufacture method therefor and application
thereof
CN105762197 A
Current assignees IPC - International classification

JIANGSU INSTITUTE OF ADVANCED INORGANIC H01L-021/34 H01L-029/24 H01L-029/43
MATERIALS* H01L-029/80*
Inventors
CPC - Cooperative classification
ZHENG RENKUI
H01L-029/24 H01L-029/43/2 H01L-029/66/969
CHEN LEI
H01L-029/80/2*
LI XIAOMIN
Priority data including date

2016CN-0216788 2016-04-08
Family
CN105762197 B 2019-01-08 CN105762197 A 2016-07-13
(CN105762197)
The invention relates to a lead magnesium niobate and lead
titanate monocrystalline-based semiconductor ferroelectric
field effect heterostructure, a manufacture method therefor
and application thereof. The semiconductor ferroelectric
field effect heterostructure comprises a substrate made up
by a lead magnesium niobate and lead titanate
monocrystalline and a channel made up by a titanium
dioxide semiconductor thin film formed on the substrate.
The general chemical formula of the titanium dioxide
semiconductor thin film is TiO2-delta, wherein 0<
Abstract
(CN105762197)
The invention relates to a lead magnesium niobate and lead titanate monocrystalline-based semiconductor ferroelectric
field effect heterostructure, a manufacture method therefor and application thereof. The semiconductor ferroelectric field
effect heterostructure comprises a substrate made up by a lead magnesium niobate and lead titanate monocrystalline and
a channel made up by a titanium dioxide semiconductor thin film formed on the substrate. The general chemical formula of
the titanium dioxide semiconductor thin film is TiO2-delta, wherein 0<
Claims
(CN105762197)
1. The semiconductor ferroelectric field effect heterostructure based on lead magnesium niobate and lead titanate single
crystals is characterized by comprising a lead magnesium niobate and lead titanate ferroelectric single crystal serving as a
substrate and a titanium dioxide semiconductor thin film formed on the substrate serving as a channel, wherein the
chemical general formula of the titanium dioxide semiconductor thin film is TiO2-Wherein 0. ltoreq. 0.2, preferably 0. ltoreq.
0.1.
2. The semiconductor ferroelectric field effect heterostructure based on lead magnesium niobate titanate single crystal as
claimed in claim 1, further comprising electrodes respectively located on one side of the lead magnesium niobate titanate
single crystal substrate and on one side of the titanium dioxide semiconductor thin film.
claimed in claim 2, wherein the electrode is metallic silver or gold.
4. The semiconductor ferroelectric field effect heterostructure based on lead magnesium niobate titanate single crystal
according to any one of claims 1 to 3, wherein the lead magnesium niobate titanate single crystal has a chemical formula of
(1-x) Pb (Mg)1/3Nb2/3)O3-xPbTiO3Wherein x is more than or equal to 0.28 and less than or equal to 0.35.
5. The semiconductor ferroelectric field effect heterostructure based on lead magnesium niobate titanate single crystals as
claimed in claim 4, characterized in that the lead magnesium niobate titanate single crystals have an orientation of (001),
(110) or (111), preferably (001).
claimed in any of claims 1 to 5, wherein the lead magnesium niobate titanate ferroelectric single crystal substrate has a
thickness of 0.05 to 1mm, and the titanium dioxide semiconductor thin film has a thickness of 10 to 500 nm.
7. A method for preparing a semiconductor ferroelectric field effect heterostructure based on lead magnesium niobate
titanate single crystal substrates as claimed in any of claims 1 to 6, characterized in that TiO is used2The ceramic block is
used as a target material and is deposited on the magnesium niobate by adopting a pulse laser deposition technologyAnd
depositing a titanium dioxide semiconductor film on the lead titanate monocrystal.
8. The method of claim 7, wherein the pulsed laser deposition process comprises evacuating the pulsed laser deposition
system cavity to a vacuum level of < 5 × 10-4Pa, heating the single crystal substrate to 400-600 ℃ as a deposition
temperature, wherein the deposition oxygen pressure is 0.01-15Pa, and controlling the thickness of the film by controlling
the deposition time, wherein the deposition time is usually 10-60 minutes, the laser energy density is 1-5J/square
centimeter, the laser frequency is 1-5Hz, and the distance between the single crystal substrate and the target is 4-7 cm.
9. The preparation method of claim 8, wherein the purity of the oxygen used in the film deposition is not less than 99.999%,
the heating rate for heating the substrate is 1-10 ℃/min, and after the deposition is finished, the titanium dioxide
semiconductor film is cooled to room temperature in situ at a cooling rate of 1-10 ℃/min.
10. A field effect device comprising a semiconductor ferroelectric field effect heterostructure based on lead magnesium
niobate titanate single crystals as claimed in any one of claims 1 to 6.
Description
(CN105762197)
TECHNICAL FIELD
The invention relates to a semiconductor ferroelectric field effect heterostructure taking lead magnesium niobate titanate
(PMN-PT for short) ferroelectric single crystal substrate as a grid and an n-type semiconductor titanium dioxide thin film as
a channel, and a preparation method and application thereof.
BACKGROUND ART
The titanium dioxide semiconductor has excellent physical, chemical, optical and mechanical properties, is a research
hotspot in the world, and has been widely applied to gas sensitive devices, solar cells, electronic devices and
magnetoelectric composite structures. Generally, titanium dioxide has three crystal structures: rutile, anatase, and brookite,
with the anatase structure being widely used. As a typical wide bandgap semiconductor, bulk titanium dioxide has a high
resistance and is in an insulating state, thereby limiting its application in electrical applications. In 2006, Nguyen Hoa Hong
et al published an article entitled "from-Temperaturesis magnetic resonance observed in unbound semiconductor and
insulating oxide thin films" in the Phys. Rev.B journal (Phys. Rev.B 2006,73,132404) which they would TiO2-Depositing the
film on (100) LaAlO3On a uniform single crystal substrate, realize TiO2-The room-temperature ferromagnetism and the
electrical conductivity of the thin film are considered to be closely related to the presence of defects such as oxygen
vacancies in the thin film. When a titanium dioxide film is deposited under low oxygen pressure, the absence of oxygen
atoms (i.e., oxygen vacancies) donates mobile electrons as charge carriers for the film, thereby enhancing the conductivity
of the film. Thus, different resistance states can be obtained by varying the film carrier concentration.
The reversible and non-volatile regulation and control of the electric field on the electrical property of the material has the
characteristics of high speed and low power consumption, has wide application prospect in a storage device, and attracts
more and more attention. The above regulation and control of the electric field to the electric property in the heterostructure
of the oxide thin film/ferroelectric single crystal substrate mainly has the following two mechanisms: lattice strain effects and
ferroelectric field effects. The lattice strain effect refers to the process that strain induced by ferroelectric polarization
reversal of a ferroelectric single crystal substrate under the action of an external electric field or induced by inverse
piezoelectric effect of the ferroelectric single crystal is transferred to the thin film in situ at an interface, so that lattice strain
of the thin film is adjusted and electric transport of the thin film is further influenced. However, the strain generated by the
polarization inversion or inverse piezoelectric effect tends to disappear or be irreversible with the disappearance of the
applied electric field, so that the influence of the applied bias electric field caused by the lattice strain effect on the electrical
properties of the film has volatility or irreversibility [ r.k.zheng et al, phys.rev.b 2007,75,212102 ]; furthermore, for some
ferroelectric single crystals with special orientation, even though the electric field can induce non-volatile lattice strain in the
ferroelectric single crystal, the induced lattice strain is usually in a metastable state (metastable), which is difficult to be
effectively controlled by the electric field [ m.liu et al, sci.rep.2013, 3,1876 ], so far the non-volatile modulation of the
electrical properties of the thin film obtained by using the metastable lattice strain in the world is only 12% at the maximum
amplitude at room temperature [ b.w.zhi et al, ACS appl.mater.inter.f.2014, 6,4603 ], which is not beneficial to practical
application. On the other hand, the ferroelectric field effect, namely the film and the ferroelectric single crystal substrate are
respectively used as a conducting channel and an insulated gate, and residual polarization in corresponding directions can
be reserved after the external electric field is removed, so that scientific basis is provided for the nonvolatile and reversible
regulation and control of the performance of the film through the electric field. The positive polarization and the negative
polarization of the ferroelectric single crystal substrate can respectively induce negative charge and positive charge on the
surface of the single crystal, so that carriers (namely electrons) of the n-type semiconductor film are accumulated and
dissipated at an interface, a carrier accumulation or dissipation layer is induced, two states of insulation or conduction of
channel resistance are realized, and the ferroelectric single crystal substrate is expected to be applied to nonvolatile, low-
power-consumption memory devices and electric control switches.
A large number of researches show that the interface coupling mechanism of a heterostructure formed by growing a
perovskite oxide thin film on a PMN-PT single crystal substrate is mainly lattice strain effect. Ferroelectric field effect is due
to the higher concentration of thin film carriers (10)21-1022/cm3) Thus the PMN-PT ferroelectric polarization causes
negligible accumulation/dissipation of film carriers. On the contrary, when the concentration of the carriers of the thin film
deposited on the ferroelectric single crystal substrate is low (10)18-1020/cm3) The formed 'thin film/ferroelectric single
crystal' heterostructure can show a remarkable ferroelectric field effect under an applied bias electric field. The ferroelectric
field effect heterostructure reported in the past is mainly to deposit an oxide diluted magnetic semiconductor film doped
with transition metal ions on a PZT film or a ferroelectric single crystal substrate. However, transition metal ion dopingThe
oxide semiconductor thin film is easy to generate composition segregation, generate enrichment of transition metal atoms
(such as ZnO doped with cobalt element: Co thin film can generate metal cobalt atom clusters in the thin film) or form
transition metal oxide (such as Co)2O3) And the like, leading to deterioration of film properties. In addition, the oxide diluted
magnetic semiconductor doped with transition metal ions has the disadvantages of complex target preparation procedure,
uneven distribution of metal ions in the target, difficult control of the valence state of the metal ions, harsh film deposition
conditions and the like.
DISCLOSURE
Disclosure of Invention
In view of the above problems, the present invention aims to provide a ferroelectric field effect heterostructure that can be
controlled by an electric field in a non-volatile and reversible manner. It is another object of the present invention to provide
a method for preparing the semiconductor ferroelectric field effect heterostructure of the present invention. It is a further
object of the present invention to provide a semiconductor device comprising the semiconductor ferroelectric field effect
heterostructure of the present invention. It is a further object of the present invention to provide a use of the semiconductor
ferroelectric field effect in the manufacture of field effect heterostructure devices.
In order to achieve the above object, the present invention provides a semiconductor ferroelectric field effect
heterostructure based on lead magnesium niobate titanate single crystal, the semiconductor ferroelectric field effect
heterostructure comprises a lead magnesium niobate titanate ferroelectric single crystal as a substrate and a titanium
dioxide semiconductor thin film formed on the substrate as a channel, the titanium dioxide semiconductor thin film has a
chemical general formula of TiO2-Wherein 0. ltoreq. 0.2, preferably 0. ltoreq. 0.1.
The ferroelectric single crystal PMN-PT has excellent ferroelectric property, and the ferroelectric polarization can be
induced by an external bias electric field, and the titanium dioxide film can be epitaxially grown on the PMN-PT single
crystal substrate by designing a preparation process. Based on the non-volatility of the ferroelectric field effect, a novel
ferroelectric field effect heterostructure with excellent performance can be obtained. The polarization phenomenon caused
by the external bias electric field in the PMN-PT single crystal substrate can cause the accumulation or dissipation of
titanium dioxide film carriers at the interface, thereby obviously changing the electric transport performance of the titanium
dioxide film. The semiconductor ferroelectric field effect heterostructure taking the PMN-PT single crystal substrate as the
grid and the titanium dioxide semiconductor film as the channel provided by the invention realizes reversible and non-
volatile regulation and control of an external bias electric field on the channel resistance, obtains two resistance states of
'on' and 'off' of the channel resistance by applying a pulse electric field, and shows brand new and excellent ferroelectric
field effect characteristics.
Preferably, the semiconductor ferroelectric field effect heterostructure based on the lead magnesium niobate titanate single
crystal further comprises electrodes which are respectively positioned on one side of the lead magnesium niobate titanate
single crystal substrate and one side of the titanium dioxide semiconductor thin film.
Also, preferably, the electrode is metallic silver or gold.
Preferably, the chemical formula of the lead magnesium niobate titanate single crystal is (1-x) Pb (Mg)1/3Nb2/3)O3-
xPbTiO3Wherein x is more than or equal to 0.28 and less than or equal to 0.35.
Preferably, the orientation of the lead magnesium niobate titanate single crystal is (001), (110) or (111), preferably (001).
Preferably, the thickness of the lead magnesium niobate titanate ferroelectric single crystal substrate is 0.05-1mm, and the
thickness of the titanium dioxide semiconductor thin film is 10-500 nm.
The invention provides a preparation method of a semiconductor ferroelectric field effect heterostructure based on a lead
magnesium niobate and lead titanate monocrystal substrate, which uses high-purity TiO2The ceramic block is used as a
target material, and a titanium dioxide semiconductor film is deposited on the lead magnesium niobate titanate single
crystal by adopting a pulse laser deposition technology.
Preferably, the process parameters of the pulsed laser deposition technique include: firstly, the cavity of the pulse laser
deposition system is vacuumized to<5×10-4Pa, heating the single crystal substrate to 400-600 ℃ as a deposition
temperature, and controlling the deposition oxygen pressure to be 0.01-15PaThe thickness of the film is controlled, the
deposition time is 10-60 minutes, the laser energy density is 1-5J/square centimeter, the laser frequency is 1-5Hz, and the
distance between the single crystal substrate and the target is 4-7 cm.
Preferably, the purity of the oxygen adopted during film deposition is more than or equal to 99.999 percent, the heating rate
of the heating substrate is 1-10 ℃/min, and after the deposition is finished, the titanium dioxide semiconductor film is
cooled to room temperature in situ, and the cooling rate is 1-10 ℃/min.
The invention provides a field effect device comprising a semiconductor ferroelectric field effect heterostructure based on
lead magnesium niobate titanate single crystals.
The invention also provides application of the semiconductor ferroelectric field effect heterostructure based on the lead
magnesium niobate titanate monocrystal in manufacturing a field effect device.
The invention has the beneficial effects that:
the invention prepares a ferroelectric field effect heterostructure taking PMN-PT ferroelectric single crystal as a substrate
and a titanium dioxide semiconductor film as a channel. The reversible and non-volatile regulation of the substrate
polarization reversal on the film resistance is realized by utilizing the in-situ and dynamic regulation and control of the
carrier concentration in the film by the surface charge generated by the polarization of the ferroelectric single crystal, and a
novel functional ferroelectric field effect heterostructure which can be obviously regulated and controlled by an electric field
is obtained and shows excellent ferroelectric field effect characteristics. Meanwhile, the invention uses pure-phase titanium
dioxide film TiO with oxygen defect2-Compared with the oxide semiconductor film doped with transition metal ions, the
preparation process and the preparation conditions are effectively simplified for the channel, the adverse factors such as
uneven film components are avoided, and the cost is saved for further application of the ferroelectric field effect
heterostructure.
DRAWINGS DESCRIPTION
FIG. 1 shows TiO prepared in an example of the present invention2-/0.71Pb(Mg1/3Nb2/3)O3-0.29PbTiO3(hereinafter
abbreviated as PMN-29PT) semiconductor ferroelectric field effect heterostructure diagram;
FIG. 2 shows TiO prepared in an example of the present invention2-The structure representation result of the/PMN-29 PT
semiconductor ferroelectric field effect heterostructure;
FIG. 3 shows TiO prepared in an example of the present invention2-The resistance-temperature (R-T) curve graphs of
the/PMN-29 PT semiconductor ferroelectric field effect heterostructure are respectively in positive and negative polarization
states of the single crystal substrate, wherein the insets are the change curves of the film carrier concentration along with
the temperature in the two polarization states;
FIG. 4 shows TiO prepared in an example of the present invention2-A graph of the relative change value of the resistance
of the/PMN-29 PT semiconductor ferroelectric field effect heterostructure under the action of a pulse electric field and time
(delta R/R-T).
INVENTION MODE
Detailed Description
The present invention is further described below in conjunction with the following embodiments and the accompanying
drawings, it being understood that the drawings and the following embodiments are illustrative of the invention only and are
not limiting.
The semiconductor ferroelectric field effect heterostructure based on the lead magnesium niobate titanate single crystal
comprises a substrate (grid) taking the lead magnesium niobate titanate ferroelectric single crystal as a substrate, a
channel (conductive channel) taking a titanium dioxide semiconductor thin film formed on the substrate and gold electrodes
(or silver electrodes or other electrodes) respectively distributed on one side of the lead magnesium niobate titanate single
crystal substrate and one side of the titanium dioxide semiconductor thin film in an evaporation mode or other modes.
Wherein, the thickness of the lead magnesium niobate titanate ferroelectric single crystal substrate can be 0.05-1 mm.
Referring to FIG. 1, TiO prepared in the examples of the present invention2-/0.71Pb(Mg1/3Nb2/3)O3-
0.29PbTiO3(hereinafter abbreviated as PMN-29PT) semiconductor ferroelectric field effect heterostructure schematic. FIG.
1 shows PMN-PT as grid, TiO2-The membrane is a channel. PMN-29The back of PT is coated with gold electrode by
evaporation, and is connected with grid lead; TiO 22-The film gold-evaporated electrode is respectively connected with the
source electrode lead and the drain electrode lead. Wherein the arrows indicate the direction of polarization, which is
defined herein as pointing towards the TiO2-The film is positively polarized, and the pointing PMN-PT back electrode is
negatively polarized.
The chemical formula of the lead magnesium niobate titanate single crystal can be (1-x) Pb (Mg)1/3Nb2/3)O3-
xPbTiO3Wherein x is more than or equal to 0.28 and less than or equal to 0.35, wherein the orientation of the lead
magnesium niobate titanate single crystal can be (001), (110) or (111), and is preferably (001). The film grown using the
(001) -oriented single crystal is optimal in the crystalline and epitaxial properties under the same production conditions.
The chemical general formula of the titanium dioxide semiconductor film is TiO2-Wherein 0. ltoreq. 0.2, preferably 0. ltoreq.
0.1. Titanium dioxide is taken as a typical wide bandgap semiconductor material, TiO grown in an oxygen-deficient
environment and with a bulk in an insulating state2-(0-0.1) oxygen vacancy exists in the film with a certain concentration,
so that the carrier concentration is 1018-1020/cm3In the range of and Ti4+The ion can obtain an electron valence of
Ti3+The ions have ferromagnetism. Thus the corresponding TiO2-the/PMN-PT heterostructure can show remarkable
ferroelectric field effect, and TiO2-Our experiments show that the carrier concentration of titanium dioxide semiconductor
film grown on PMN-PT ferroelectric single crystal substrate is about 1-8 × 1018/cm3Built TiO2-The interface coupling
mechanism of the/PMN-PT heterostructure is mainly a ferroelectric field effect. Wherein the thickness of the titanium
dioxide semiconductor film can be 10-500 nm.
According to the invention, the titanium dioxide semiconductor film is directly grown on the lead magnesium niobate titanate
ferroelectric single crystal substrate, so that the preparation process is simplified, and good interface quality and higher
working efficiency are obtained. Because the lead magnesium niobate titanate ferroelectric single crystal has excellent
ferroelectric performance, the ferroelectric polarization induced by the bias electric field enables the surface of the
ferroelectric single crystal to generate positive or negative charges, thereby inducing the change of the carrier
concentration of the titanium dioxide film, and further enabling the channel resistance of the film to be obviously changed,
and further obtaining a novel functional ferroelectric field effect heterostructure with obvious electric field adjustable
characteristic. The preparation method of the semiconductor ferroelectric field effect heterostructure based on lead
magnesium niobate titanate single crystal provided by the invention is exemplarily illustrated below.
In the invention, TiO is used2The ceramic block is used as a target material, and the pulsed laser deposition technology is
adopted to deposit on a lead magnesium niobate lead titanate single crystal substrate to obtain TiO2-A semiconductor thin
film. Wherein, the film is TiO2-The mid-oxygen deficiency results from a lower oxygen pressure of the deposit, and thus the
TiO can be adjusted by controlling the oxygen pressure of the deposit2-The oxygen vacancy concentration of the
semiconductor film changes the carrier concentration and the conductivity of the semiconductor film.
The process parameters of the pulsed laser deposition technology include, but are not limited to, firstly evacuating the
cavity of the pulsed laser deposition system to < 5 × 10-4Pa, heating the single crystal substrate to 400-600 ℃ as a
deposition temperature, wherein the deposition oxygen pressure is 0.01-15Pa, and controlling the thickness of the film by
controlling the deposition time, wherein the deposition time is usually 10-60 minutes, the laser energy density is 1-
5J/square centimeter, the laser frequency is 1-5Hz, and the distance between the single crystal substrate and the target is
4-7 cm.
Wherein, the purity of the oxygen used in the film deposition is more than or equal to 99.999 percent, the heating rate of the
heating substrate can be 1-10 ℃/min, and after the deposition is finished, the titanium dioxide semiconductor film is cooled
to the room temperature in situ, and the cooling rate can be 1-10 ℃/min.
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.
INVENTION MODE
Example TiO2-/0.71Pb(Mg1/3Nb2/3)O3-0.29PbTiO3(PMN-29 PT for short) preparation of semiconductor ferroelectric field
effect heterostructure, in which PMN-29PT is oriented in (001).
Preparing a film: high purity TiO2The ceramic block is used as a target material, pulse laser deposition is carried out on a
PMN-29PT single crystal substrate with a polished single surface, and the TiO is obtained2-The PMN-29PT semiconductor
ferroelectric field effect heterostructure is prepared by placing a single-side polished (001) oriented PMN-29PT single
crystal substrate into a reaction chamber of a pulsed laser deposition system, and vacuumizing the background of the
reaction chamber to less than 5 × 10-4Pa, and heating the substrate to 600 deg.C, and evacuating the reaction chamber to
less than 5 × 10-4Pa, and filling oxygen gas until the deposition oxygen pressure is 0.5Pa, the laser energy is 3J/square
centimeter, the laser frequency is 5Hz, the distance between the substrate and the target material is 5 centimeters, and the
deposition time is 20 minutes to obtain the TiO2-The film thickness was 148 nm.
The high purity TiO2The purity of the ceramic target is more than 99.99 percent, and the relative density is more than 97
percent.
The purity of the deposited oxygen is more than 99.999 percent, the influence of impurities brought by the environment can
be minimized by adopting high-purity oxygen, and the quality of the prepared film is improved.
The heating rate of the substrate is 1-10 deg.C/min.
After the deposition is finished, the prepared TiO2-the/PMN-29 PT semiconductor ferroelectric field effect heterostructure is
cooled to room temperature in situ at the cooling rate of 1-10 ℃/min.
Preparing an electrode: using PMN-29PT monocrystal substrate as grid electrode, evaporating gold-plated electrode on
back surface of substrate, connecting grid electrode lead and using TiO2-A schematic diagram of a semiconductor
ferroelectric field effect heterostructure constructed with a thin film as a channel, a gold thin film as a source and a drain
deposited as a source and a drain lead respectively, is shown in FIG. 1, wherein the arrows indicate the polarization
direction, which is defined herein to point at TiO2-The film is positively polarized, and the pointing PMN-PT back electrode
is negatively polarized. Wherein the PMN-29PT single crystal substrate is oriented to (001); thickness of the substrate:
0.5mm, and 5mm in length and width; TiO 22-Film thickness: 148nm, gold electrode thickness: 100 nm.
Structural characterization: the following tests were performed on the prepared semiconductor ferroelectric field effect
heterostructure, and the results are shown in fig. 2: FIG. 2 shows TiO prepared in an example of the present invention2-
The structure characterization result of the/PMN-29 PT semiconductor ferroelectric field effect heterostructure. Fig. 2(a) is
an X-ray diffraction (XRD) pattern measured at room temperature, and it can be found that PMN-29PT (00l) (l ═ 1,2,3) and
TiO are excluded2-(00l) (l ═ 4,8) no other peaks appeared, indicating that the film was monophasic and grown with c-axis
orientation.
FIGS. 2(b) and 2(c) are each TiO2-Phi scan of the thin film and PMN-29PT single crystal substrate (101) plane, showing
TiO2-The thin film is epitaxially grown on a PMN-29PT single crystal substrate.
Characterization of electrotransport properties: FIG. 3 shows TiO prepared in an example of the present invention2-The
resistance-temperature (R-T) curve graph of the film of the/PMN-29 PT semiconductor ferroelectric field effect
heterostructure is obtained when the single crystal substrate is in a positive polarization state and a negative polarization
state, wherein the insets are the change curves of the carrier concentration of the film with the temperature of the substrate
in the positive polarization state and the negative polarization state respectively. From fig. 3, it can be seen that, in the
temperature range measured, the sheet resistance of the substrate in the negative polarization state is greater than that of
the substrate in the positive polarization state, and accordingly, the carrier concentration of the former is significantly lower
than that of the latter, indicating that the TiO is present2-the/PMN-29 PT semiconductor ferroelectric field effect
heterostructure realizes obvious regulation and control of an external bias electric field on channel resistance and realizes
different resistance states of the film when the substrate is in different polarization states.
FIG. 4 shows a temperature of 3TiO prepared in the examples of the invention at 00K2-Resistance-time curve diagram
of/PMN-29 PT semiconductor ferroelectric field effect heterostructure under action of positive and negative pulse electric
field. It can be seen from FIG. 4 that the application of positive and negative pulse electric fields can respectively obtain two
resistance states of "on" and "off", indicating that the application of an external bias electric field can realize the application
of the TiO2-Reversible and non-volatile regulation and control of channel resistance of the/PMN-29 PT semiconductor
ferroelectric field effect heterostructure.
(CN105762197)
技术领域
本发明涉及一种包括铌镁酸铅钛酸铅( 简称PMN - PT ) 铁电单晶衬底作为栅极和n 型半导体二氧化钛薄膜作为沟道的半导体
铁电场效应异质结构及其制备方法和应用。
背景技术
二氧化钛半导体具有优异的物理、化学、光学及机械等性能, 一直是国际上的研究热点, 并已广泛应用于气敏器件、太阳能电
池、电子器件以及磁电复合结构中。通常, 二氧化钛具有三种晶体结构: 金红石、锐钛矿以及板钛矿, 其中以锐钛矿结构应用
广泛。作为典型的宽禁带半导体, 块体二氧化钛电阻大, 呈绝缘态, 因而限制了其在电学方面的应用。2006年 , Nguyen Hoa
Hong 等人在Phys . Rev . B 杂志上发表了题为“Room - Temperatureferromagnetism observed in undoped semiconducting
and insulating oxide thin films ”的文章( Phys . Rev . B 2006,73,132404 ) , 他们将TiO 2- δ 薄膜沉积在(
100 ) LaAlO 3 等单晶衬底上, 实现了TiO 2- δ 薄膜的室温铁磁性和导电性, 这一铁磁性和
导电性被认为与薄膜中存在氧空位等缺陷密切相关。当二氧化钛薄膜在低氧压下沉积时, 氧原子的缺失( 即氧空位) 会贡献出
可以移动的电子, 成为薄膜的载流子, 从而增强薄膜的导电性。因此, 可以通过改变薄膜载流子浓度获得不同的电阻状态。
电场对材料电学性能的可逆、非挥发调控具有速度快、功耗低的特点, 在存储器件中具有广阔的应用前景, 吸引了越来越多的
关注。在“氧化物薄膜/ 铁电单晶衬底”异质结构中实现电场对电学性能的上述调控主要有以下两种机理: 晶格应变效应和铁电
场效应。其中, 晶格应变效应是指铁电单晶衬底在外加电场作用下铁电极化翻转诱导的或由于铁电单晶的逆压电效应诱导的应
变在界面处原位传递给薄膜, 进而调节薄膜的晶格应变并进一步影响其电输运的过程。然而, 极化翻转或者逆压电效应产生的
应变往往随着外加电场的消失而消失或者具有不可逆性, 因而由晶格应变效应引起的外加偏置电场对薄膜电学性能的影响具有
易失性或不可逆性【R . K . Zheng et al , Phys . Rev . B 2007,75,212102 】; 再者, 对于某些特殊取向的铁电单晶, 即使电场
能够在铁电单晶中诱导出非挥发性的晶格应变, 然而这种诱导的晶格应变通常处于亚稳态( metastable ) , 很难通过电场进行有
效控制【M . Liu et al , Sci . Reps . 2013,3,1876 】, 迄今为止国际上利用这种亚稳态的晶格应变获得的薄膜电学性能非挥发
性调控在室温下的最大幅度仅为12% 【B . W . Zhi et al . , ACS Appl . Mater . Interf . 2014,6,4603 】, 不利于实际应用。另
一方面, 铁电场效应—薄膜和铁电单晶衬底分别作为导电沟道和绝缘栅极——由于撤除外加电场后相应方向的剩余极化可以保
留, 这为通过电场非易失、可逆地调控薄膜的性能提供了科学依据。铁电单晶衬底正向和负向极化可分别在单晶表面处诱导负
电荷和正电荷, 导致n 型半导体薄膜的载流子( 即电子) 在界面处出现累积和耗散, 从而诱导出载流子累积或耗散层, 实现沟道
电阻的“绝缘”或“导通”两种状态, 有望应用于非易失性、低功耗存储器件及电控开关。
大量的研究表明, 在PMN - PT 单晶衬底上生长钙钛矿氧化物薄膜所构成的异质结构的界面耦合机制主要为晶格应变效应。铁
电场效应则由于薄膜载流子浓度较高( 10 21 - 10 22 / cm 3 ) , 因而
PMN - PT 铁电极化引起薄膜载流子的累积/ 耗散可以忽略不计。相反地, 当沉积在铁电单晶衬底上的薄膜载流子浓度较低时(
10 18 - 10 20 / cm 3 ) , 所构成的“薄膜/ 铁电单晶”异质结构在外加偏
置电场下将表现出显著的铁电场效应。以往报道的铁电场效应异质结构主要是将过渡金属离子掺杂的氧化物稀磁半导体薄膜
沉积在PZT 薄膜或铁电单晶衬底上。然而, 过渡金属离子掺杂的氧化物半导体薄膜容易出现成分偏析, 产生过渡金属原子富集
( 如钴元素掺杂的ZnO : Co 薄膜会在薄膜中产生金属钴原子团簇) 或形成过渡金属氧化物( 如Co 2 O 3 ) 等杂相, 导致薄膜性能恶化。此外, 过渡金属离子掺杂的氧化物稀磁半导体存在靶材制备程序复杂, 金属离子在
靶材中分布不均匀, 金属离子价态难以控制, 薄膜沉积条件苛刻等不利条件。
发明内容
针对上述问题, 本发明旨在提供一种可由电场进行非挥发性、可逆调控的铁电场效应异质结构。本发明的另一个目的在于, 提
供一种制备本发明所述半导体铁电场效应异质结构的方法。本发明的又一个目的在于, 提供一种包含本发明所述半导体铁电场
效应异质结构的半导体装置。本发明的再一个目的在于, 提供了一种所述半导体铁电场效应在制造场效应异质结构装置中的应
用。
为了达到上述目的, 本发明提供了一种基于铌镁酸铅钛酸铅单晶的半导体铁电场效应异质结构, 所述半导体铁电场效应异质结
构包括以铌镁酸铅钛酸铅铁电单晶作为衬底和以形成于所述衬底上的二氧化钛半导体薄膜作为沟道( channel ) , 所述二氧化钛
半导体薄膜的化学通式为TiO 2- δ , 其中0 ≤δ≤0.2, 优选为0 ≤δ≤0.1 。
铁电单晶PMN - PT 具有优良的铁电性能, 外加偏置电场可诱导其产生铁电极化, 且可以通过设计制备工艺, 使得二氧化钛薄
膜在PMN - PT 单晶衬底上外延生长。基于铁电场效应的非挥发性, 能够获得性能优异的新型铁电场效应异质结构。外加偏置
电场在PMN - PT 单晶衬底中引起的极化现象可引起二氧化钛薄膜载流子在界面的累积或耗散, 从而显著改变二氧化钛薄膜的
电输运性能。本发明给出的以PMN - PT 单晶衬底为栅极、二氧化钛半导体薄膜为沟道的半导体铁电场效应异质结构, 实现了
外加偏置电场对沟道电阻的可逆、非挥发调控, 且通过施加脉冲电场获得了沟道电阻的“开”和“关”两种电阻态, 表现出了全新且
优良的铁电场效应特征。
较佳地, 所述基于铌镁酸铅钛酸铅单晶的半导体铁电场效应异质结构还包括电极, 所述的电极分别位于铌镁酸铅钛酸铅单晶衬
底的一侧和二氧化钛半导体薄膜一侧。
又, 较佳地, 所述电极为金属银或金。
较佳地, 所述铌镁酸铅钛酸铅单晶的化学式为( 1- x ) Pb ( Mg 1/3 Nb 2/3 ) O 3
 - xPbTiO 3 , 其中, 0.28 ≤x ≤0.35 。
较佳地, 所述铌镁酸铅钛酸铅单晶的取向为( 001 ) 、( 110 ) 或( 111 ) , 优选为( 001 ) 。
较佳地, 所述铌镁酸铅钛酸铅铁电单晶衬底厚度为0.05-1 mm , 所述二氧化钛半导体薄膜的厚度为10-500 nm 。
本发明提供了一种基于铌镁酸铅钛酸铅单晶衬底的半导体铁电场效应异质结构的制备方法, 以高纯度的TiO 2 陶瓷块体为靶材, 采用脉冲激光沉积技术在铌镁酸铅钛酸铅单晶上沉积二氧化钛半导体薄膜。
较佳地, 所述脉冲激光沉积技术的工艺参数包括: 先将脉冲激光沉积系统腔体抽真空至& lt ; 5 ×10 - 4 Pa ,
加热单晶衬底至400-600 ℃作为沉积温度, 沉积氧压为0.01-15 Pa , 通过控制沉积时间实现控制薄膜的厚度, 通常的沉积时间
为10-60 分钟, 激光能量密度为1-5 J / 平方厘米, 激光频率为1-5 Hz , 单晶衬底与靶之间的距离为4-7 厘米。
较佳地, 所述沉积薄膜时采用的氧气纯度≥99.999%, 加热衬底的升温速率为1-10 ℃/ 分钟, 沉积结束后, 所述二氧化钛半导体
薄膜原位冷却至室温, 降温速率为1-10 ℃/ 分钟。
本发明提供了一种包含基于铌镁酸铅钛酸铅单晶的半导体铁电场效应异质结构的场效应装置。
本发明还提供了一种基于铌镁酸铅钛酸铅单晶的半导体铁电场效应异质结构在制造场效应装置中的应用。
本发明的有益效果:
本发明制备了一种以PMN - PT 铁电单晶为衬底、二氧化钛半导体薄膜为沟道的铁电场效应异质结构。利用铁电单晶极化产
生的表面电荷原位、动态调控薄膜中的载流子浓度, 实现了衬底极化翻转对薄膜电阻的可逆、非挥发调控, 获得了可由电场显
著调控的新型功能铁电场效应异质结构, 该铁电场效应异质结构表现出了优良的铁电场效应特征。同时, 本发明以具有氧缺陷
的纯相二氧化钛薄膜TiO 2- δ 为沟道, 相较于过渡金属离子掺杂的氧化物半导体薄膜有效地简化了制备过程
与制备条件, 同时避免了薄膜成分不均匀等不利因素, 为铁电场效应异质结构的进一步应用节约了成本。
附图说明
图1 为本发明实施例中制备的TiO 2- δ / 0.71 Pb ( Mg 1/3 Nb 2/3 ) O
 3 - 0.29 PbTiO 3 ( 以下简称为PMN - 29 PT ) 半导体铁电场效应异质结构示意图;
图2 为本发明实施例中制备的TiO 2- δ / PMN - 29 PT 半导体铁电场效应异质结构的结构表征结果;
图3 为本发明实施例中制备的TiO 2- δ / PMN - 29 PT 半导体铁电场效应异质结构在单晶衬底分别处于正、
负极化态时的电阻- 温度( R - T ) 曲线图, 其中, 插图为上述两种极化态下薄膜载流子浓度随温度的变化曲线;
图4 为本发明实施例中制备的TiO 2- δ / PMN - 29 PT 半导体铁电场效应异质结构在脉冲电场作用下的电阻
的相对变化值- 时间( ΔR / R - T ) 曲线图。
具体实施方式
以下结合附图和下述实施方式进一步说明本发明, 应理解, 附图及下述实施方式仅用于说明本发明, 而非限制本发明。
本发明提供的基于铌镁酸铅钛酸铅单晶的半导体铁电场效应异质结构包括以铌镁酸铅钛酸铅铁电单晶作为的衬底( 栅极) 、以
形成于所述衬底上的二氧化钛半导体薄膜作为的沟道( 导电沟道) 和分别以蒸镀的方式或其他方式分布在铌镁酸铅钛酸铅单晶
衬底的一侧和二氧化钛半导体薄膜一侧的金电极( 或银电极、或其他电极) 。其中, 所述铌镁酸铅钛酸铅铁电单晶衬底厚度可
为0.05-1 mm 。参见图1 为本发明实施例中制备的TiO 2- δ / 0.71 Pb ( Mg 1/3 Nb 2/3 ) O 3 - 0.29 PbTiO 3 ( 以下简称为PMN - 29 PT ) 半导体铁电场效应异
质结构示意图。图1 所示以PMN - PT 为栅极, TiO 2- δ 薄膜为沟道。PMN - 29 PT 背面蒸镀金电极, 接栅极
引线; TiO 2- δ 薄膜蒸镀金电极, 分别接源极、漏极引线。其中的箭头表示极化方向, 这里定义极化方向指向
TiO 2- δ 薄膜为正极化, 指向PMN - PT 背电极为负极化。
上述铌镁酸铅钛酸铅单晶的化学式可为( 1- x ) Pb ( Mg 1/3 Nb 2/3 ) O 3 - xPbTiO 3 , 其中, 0.28 ≤x ≤0.35, 其中所述铌镁酸铅钛酸铅单晶的取向可为( 001 ) 、( 110 ) 或( 111
) , 优选为( 001 ) 。在相同制备条件下, 使用( 001 ) 取向的单晶生长的薄膜结晶性能和外延性能最佳。
上述二氧化钛半导体薄膜的化学通式为TiO 2- δ , 其中0 ≤δ≤0.2, 优选为0 ≤δ≤0.1 。二氧化钛作为一种典型
的宽禁带半导体材料, 块体呈绝缘态, 但在缺氧环境下生长的TiO 2- δ ( 0 ≤δ≤0.1 ) 薄膜会存在一定浓度的氧
空位, 导致其载流子浓度处于10 18 - 10 20 / cm 3 范围, 且Ti 
4 + 离子可以获得一个电子变价为Ti 3 + 离子而具有铁磁性。因而相应的TiO 2- δ / PMN - PT 异质结构能够表现出显著的铁电场效应, 且TiO 2- δ 薄膜具有铁磁性。我们的大量实验表明,
在PMN - PT 铁电单晶衬底上生长二氧化钛半导体薄膜的载流子浓度大约为1-8 ×10 18 / cm 3 , 所构建的TiO 2- δ / PMN - PT 异质结构的界面耦合机制主要为铁电场效应。其中, 所述二氧化钛半
导体薄膜的厚度可为10-500 nm 。
根据本发明, 在铌镁酸铅钛酸铅铁电单晶衬底上直接生长二氧化钛半导体薄膜, 不仅简化了制备工艺, 而且获得了良好的界面
质量和较高的工作效率。由于铌镁酸铅钛酸铅铁电单晶具有优异的铁电性能, 偏置电场诱导的铁电极化使得铁电单晶表面产生
正或负电荷, 从而诱导二氧化钛薄膜的载流子浓度出现改变, 从而使得薄膜的沟道电阻发生显著改变, 进而获得了具有显著电
场可调节特性的新型功能铁电场效应异质结构。以下示例性地说明本发明提供的基于铌镁酸铅钛酸铅单晶的半导体铁电场效
应异质结构的制备方法。
本发明以TiO 2 陶瓷块体为靶材, 采用脉冲激光沉积技术在铌镁酸铅钛酸铅单晶衬底上进行沉积, 得到TiO
 2- δ 半导体薄膜。其中, 薄膜TiO 2- δ 中氧的缺失来源于较低的沉积氧压, 因此可通过控
制沉积氧压调节所述TiO 2- δ 半导体薄膜的氧空位浓度, 改变其载流子浓度和导电性能。
上述脉冲激光沉积技术的工艺参数包括但不仅限于: 先将脉冲激光沉积系统腔体抽真空至& lt ; 5 ×10 - 4 
Pa , 加热单晶衬底至400-600 ℃作为沉积温度, 沉积氧压为0.01-15 Pa , 通过控制沉积时间实现控制薄膜的厚度, 通常的沉积
时间为10-60 分钟, 激光能量密度为1-5 J / 平方厘米, 激光频率为1-5 Hz , 单晶衬底与靶之间的距离为4-7 厘米。
其中, 沉积薄膜时采用的氧气纯度≥99.999%, 加热衬底的升温速率可为1-10 ℃/ 分钟, 沉积结束后, 所述二氧化钛半导体薄膜
原位冷却至室温, 降温速率可为1-10 ℃/ 分钟。
下面进一步例举实施例以详细说明本发明。同样应理解, 以下实施例只用于对本发明进行进一步说明, 不能理解为对本发明保
护范围的限制, 本领域的技术人员根据本发明的上述内容作出的一些非本质的改进和调整均属于本发明的保护范围。下述示例
具体的工艺参数等也仅是合适范围中的一个示例, 即本领域技术人员可以通过本文的说明做合适的范围内选择, 而并非要限定
于下文示例的具体数值。
实施例TiO 2- δ / 0.71 Pb ( Mg 1/3 Nb 2/3 ) O 3 -
0.29 PbTiO 3 ( 简称为PMN - 29 PT ) 半导体铁电场效应异质结构的制备, 其中PMN - 29 PT 的取向为( 001
)。
薄膜制备: 高纯TiO 2 陶瓷块为靶材, 在单面抛光过的PMN - 29 PT 单晶衬底上进行脉冲激光沉积, 得到所
述TiO 2- δ / PMN - 29 PT 半导体铁电场效应异质结构, 其中, 脉冲激光沉积技术的参数为: 将单面抛光过的(
001 ) 取向的PMN - 29 PT 单晶衬底放入脉冲激光沉积系统反应腔体中, 将脉冲激光沉积系统腔体本底真空抽至小于5 ×10 - 4 Pa , 并加热衬底至600 ℃, 再将反应室真空抽至小于5 ×10 - 4 Pa , 并充入氧气至沉积
氧压0.5 Pa , 激光能量为3 J / 平方厘米, 激光频率为5 Hz , 衬底与靶材间距为5 厘米, 沉积时间为20 分钟, 得到所述TiO 2- δ 薄膜厚度为148 nm 。
所述高纯TiO 2 陶瓷靶材的纯度大于99.99%, 相对密度大于97% 。
所述沉积氧气纯度& gt ; 99.999%, 采用高纯氧气可将环境带入的杂质影响降到最低, 提高制备薄膜的质量。
衬底加热时的升温速率为1-10 ℃/ 分钟。
沉积结束后, 将制得的所述TiO 2- δ / PMN - 29 PT 半导体铁电场效应异质结构以1-10 ℃/ 分钟的降温速率
原位冷却至室温。
电极制备: 以PMN - 29 PT 单晶衬底作为栅极, 在衬底背面蒸镀金电极, 接栅极引线, 以TiO 2- δ 薄膜作为沟
道, 蒸镀金薄膜作为源极和漏极, 分别接源极和漏极引线, 所构建的半导体铁电场效应异质结构的示意图示于图1, 其中的箭头
表示极化方向, 这里定义极化方向指向TiO 2- δ 薄膜为正极化, 指向PMN - PT 背电极为负极化。其中, PMN
- 29 PT 单晶衬底取向为( 001 ) ; 衬底厚度: 0.5 mm , 长度、宽度均为5 mm ; TiO 2- δ 薄膜厚度: 148 nm ,
金电极厚度: 100 nm 。
结构表征: 对所制得的半导体铁电场效应异质结构进行了以下测试, 结果示于图2 中: 图2 为本发明实施例中制备的TiO 2- δ / PMN - 29 PT 半导体铁电场效应异质结构的结构表征结果。图2 ( a ) 为在室温下测得的X 射线衍射( XRD )
图谱, 可以发现, 除了PMN - 29 PT ( 00 l ) ( l = 1,2,3 ) 和TiO 2- δ ( 00 l ) ( l = 4,8 ) 的衍射峰外, 没有其他峰
出现, 表明薄膜为单相且沿c 轴取向生长。
图2 ( b ) 和2 ( c ) 分别为TiO 2- δ 薄膜和PMN - 29 PT 单晶衬底( 101 ) 面的phi 扫描图, 表明TiO 
2- δ 薄膜外延生长在PMN - 29 PT 单晶衬底上。
电输运性质表征: 图3 为本发明实施例中制备的TiO 2- δ / PMN - 29 PT 半导体铁电场效应异质结构在单晶
衬底处于正、负极化态时薄膜的电阻- 温度( R - T ) 曲线图, 其中, 插图为衬底分别出于正、负极化态下薄膜的载流子浓度随温
度的变化曲线。从图3 可以发现, 在测量温度区间内, 衬底处于负极化态时薄膜电阻均大于衬底处于正极化态时薄膜电阻, 相应
地, 前者载流子浓度显著低于后者, 表明所述TiO 2- δ / PMN - 29 PT 半导体铁电场效应异质结构实现了外加
偏置电场对沟道电阻的显著调控, 实现了衬底处于不同极化状态下薄膜的不同电阻态。
图4 为温度为300 K 时本发明实施例中制备的TiO 2- δ / PMN - 29 PT 半导体铁电场效应异质结构在正、负
脉冲电场作用下的电阻- 时间曲线图。从图4 可以看出施加正向和负向脉冲电场分别可得到“导通”、“绝缘”两个电阻态, 即“开
”和“关”, 表明外加偏置电场可以实现对所述TiO 2- δ / PMN - 29 PT 半导体铁电场效应异质结构的沟道电阻
的可逆、非挥发调控。
English description
(CN105762197)
TECHNICAL FIELD
The invention relates to a semiconductor ferroelectric field effect heterostructure taking lead magnesium niobate titanate
(PMN-PT for short) ferroelectric single crystal substrate as a grid and an n-type semiconductor titanium dioxide thin film as
a channel, and a preparation method and application thereof.
BACKGROUND ART
The titanium dioxide semiconductor has excellent physical, chemical, optical and mechanical properties, is a research
hotspot in the world, and has been widely applied to gas sensitive devices, solar cells, electronic devices and
magnetoelectric composite structures. Generally, titanium dioxide has three crystal structures: rutile, anatase, and brookite,
with the anatase structure being widely used. As a typical wide bandgap semiconductor, bulk titanium dioxide has a high
resistance and is in an insulating state, thereby limiting its application in electrical applications. In 2006, Nguyen Hoa Hong
et al published an article entitled "from-Temperaturesis magnetic resonance observed in unbound semiconductor and
insulating oxide thin films" in the Phys. Rev.B journal (Phys. Rev.B 2006,73,132404) which they would TiO2-Depositing the
film on (100) LaAlO3On a uniform single crystal substrate, realize TiO2-The room-temperature ferromagnetism and the
electrical conductivity of the thin film are considered to be closely related to the presence of defects such as oxygen
vacancies in the thin film. When a titanium dioxide film is deposited under low oxygen pressure, the absence of oxygen
atoms (i.e., oxygen vacancies) donates mobile electrons as charge carriers for the film, thereby enhancing the conductivity
of the film. Thus, different resistance states can be obtained by varying the film carrier concentration.
The reversible and non-volatile regulation and control of the electric field on the electrical property of the material has the
characteristics of high speed and low power consumption, has wide application prospect in a storage device, and attracts
more and more attention. The above regulation and control of the electric field to the electric property in the heterostructure
of the oxide thin film/ferroelectric single crystal substrate mainly has the following two mechanisms: lattice strain effects and
ferroelectric field effects. The lattice strain effect refers to the process that strain induced by ferroelectric polarization
reversal of a ferroelectric single crystal substrate under the action of an external electric field or induced by inverse
piezoelectric effect of the ferroelectric single crystal is transferred to the thin film in situ at an interface, so that lattice strain
of the thin film is adjusted and electric transport of the thin film is further influenced. However, the strain generated by the
polarization inversion or inverse piezoelectric effect tends to disappear or be irreversible with the disappearance of the
applied electric field, so that the influence of the applied bias electric field caused by the lattice strain effect on the electrical
properties of the film has volatility or irreversibility [ r.k.zheng et al, phys.rev.b 2007,75,212102 ]; furthermore, for some
ferroelectric single crystals with special orientation, even though the electric field can induce non-volatile lattice strain in the
ferroelectric single crystal, the induced lattice strain is usually in a metastable state (metastable), which is difficult to be
effectively controlled by the electric field [ m.liu et al, sci.rep.2013, 3,1876 ], so far the non-volatile modulation of the
electrical properties of the thin film obtained by using the metastable lattice strain in the world is only 12% at the maximum
amplitude at room temperature [ b.w.zhi et al, ACS appl.mater.inter.f.2014, 6,4603 ], which is not beneficial to practical
application. On the other hand, the ferroelectric field effect, namely the film and the ferroelectric single crystal substrate are
respectively used as a conducting channel and an insulated gate, and residual polarization in corresponding directions can
be reserved after the external electric field is removed, so that scientific basis is provided for the nonvolatile and reversible
regulation and control of the performance of the film through the electric field. The positive polarization and the negative
polarization of the ferroelectric single crystal substrate can respectively induce negative charge and positive charge on the
surface of the single crystal, so that carriers (namely electrons) of the n-type semiconductor film are accumulated and
dissipated at an interface, a carrier accumulation or dissipation layer is induced, two states of insulation or conduction of
channel resistance are realized, and the ferroelectric single crystal substrate is expected to be applied to nonvolatile, low-
power-consumption memory devices and electric control switches.
A large number of researches show that the interface coupling mechanism of a heterostructure formed by growing a
perovskite oxide thin film on a PMN-PT single crystal substrate is mainly lattice strain effect. Ferroelectric field effect is due
to the higher concentration of thin film carriers (10)21-1022/cm3) Thus the PMN-PT ferroelectric polarization causes
negligible accumulation/dissipation of film carriers. On the contrary, when the concentration of the carriers of the thin film
deposited on the ferroelectric single crystal substrate is low (10)18-1020/cm3) The formed 'thin film/ferroelectric single
crystal' heterostructure can show a remarkable ferroelectric field effect under an applied bias electric field. The ferroelectric
field effect heterostructure reported in the past is mainly to deposit an oxide diluted magnetic semiconductor film doped
with transition metal ions on a PZT film or a ferroelectric single crystal substrate. However, transition metal ion dopingThe
oxide semiconductor thin film is easy to generate composition segregation, generate enrichment of transition metal atoms
(such as ZnO doped with cobalt element: Co thin film can generate metal cobalt atom clusters in the thin film) or form
transition metal oxide (such as Co)2O3) And the like, leading to deterioration of film properties. In addition, the oxide diluted
magnetic semiconductor doped with transition metal ions has the disadvantages of complex target preparation procedure,
uneven distribution of metal ions in the target, difficult control of the valence state of the metal ions, harsh film deposition
conditions and the like.
DISCLOSURE
Disclosure of Invention
In view of the above problems, the present invention aims to provide a ferroelectric field effect heterostructure that can be
controlled by an electric field in a non-volatile and reversible manner. It is another object of the present invention to provide
a method for preparing the semiconductor ferroelectric field effect heterostructure of the present invention. It is a further
object of the present invention to provide a semiconductor device comprising the semiconductor ferroelectric field effect
heterostructure of the present invention. It is a further object of the present invention to provide a use of the semiconductor
ferroelectric field effect in the manufacture of field effect heterostructure devices.
In order to achieve the above object, the present invention provides a semiconductor ferroelectric field effect
heterostructure based on lead magnesium niobate titanate single crystal, the semiconductor ferroelectric field effect
heterostructure comprises a lead magnesium niobate titanate ferroelectric single crystal as a substrate and a titanium
dioxide semiconductor thin film formed on the substrate as a channel, the titanium dioxide semiconductor thin film has a
chemical general formula of TiO2-Wherein 0. ltoreq. 0.2, preferably 0. ltoreq. 0.1.
The ferroelectric single crystal PMN-PT has excellent ferroelectric property, and the ferroelectric polarization can be
induced by an external bias electric field, and the titanium dioxide film can be epitaxially grown on the PMN-PT single
crystal substrate by designing a preparation process. Based on the non-volatility of the ferroelectric field effect, a novel
ferroelectric field effect heterostructure with excellent performance can be obtained. The polarization phenomenon caused
by the external bias electric field in the PMN-PT single crystal substrate can cause the accumulation or dissipation of
titanium dioxide film carriers at the interface, thereby obviously changing the electric transport performance of the titanium
dioxide film. The semiconductor ferroelectric field effect heterostructure taking the PMN-PT single crystal substrate as the
grid and the titanium dioxide semiconductor film as the channel provided by the invention realizes reversible and non-
volatile regulation and control of an external bias electric field on the channel resistance, obtains two resistance states of
'on' and 'off' of the channel resistance by applying a pulse electric field, and shows brand new and excellent ferroelectric
field effect characteristics.
Preferably, the semiconductor ferroelectric field effect heterostructure based on the lead magnesium niobate titanate single
crystal further comprises electrodes which are respectively positioned on one side of the lead magnesium niobate titanate
single crystal substrate and one side of the titanium dioxide semiconductor thin film.
Also, preferably, the electrode is metallic silver or gold.
Preferably, the chemical formula of the lead magnesium niobate titanate single crystal is (1-x) Pb (Mg)1/3Nb2/3)O3-
xPbTiO3Wherein x is more than or equal to 0.28 and less than or equal to 0.35.
Preferably, the orientation of the lead magnesium niobate titanate single crystal is (001), (110) or (111), preferably (001).
Preferably, the thickness of the lead magnesium niobate titanate ferroelectric single crystal substrate is 0.05-1mm, and the
thickness of the titanium dioxide semiconductor thin film is 10-500 nm.
The invention provides a preparation method of a semiconductor ferroelectric field effect heterostructure based on a lead
magnesium niobate and lead titanate monocrystal substrate, which uses high-purity TiO2The ceramic block is used as a
target material, and a titanium dioxide semiconductor film is deposited on the lead magnesium niobate titanate single
crystal by adopting a pulse laser deposition technology.
Preferably, the process parameters of the pulsed laser deposition technique include: firstly, the cavity of the pulse laser
deposition system is vacuumized to<5×10-4Pa, heating the single crystal substrate to 400-600 ℃ as a deposition
temperature, and controlling the deposition oxygen pressure to be 0.01-15PaThe thickness of the film is controlled, the
deposition time is 10-60 minutes, the laser energy density is 1-5J/square centimeter, the laser frequency is 1-5Hz, and the
distance between the single crystal substrate and the target is 4-7 cm.
Preferably, the purity of the oxygen adopted during film deposition is more than or equal to 99.999 percent, the heating rate
of the heating substrate is 1-10 ℃/min, and after the deposition is finished, the titanium dioxide semiconductor film is
cooled to room temperature in situ, and the cooling rate is 1-10 ℃/min.
The invention provides a field effect device comprising a semiconductor ferroelectric field effect heterostructure based on
lead magnesium niobate titanate single crystals.
The invention also provides application of the semiconductor ferroelectric field effect heterostructure based on the lead
magnesium niobate titanate monocrystal in manufacturing a field effect device.
The invention has the beneficial effects that:
the invention prepares a ferroelectric field effect heterostructure taking PMN-PT ferroelectric single crystal as a substrate
and a titanium dioxide semiconductor film as a channel. The reversible and non-volatile regulation of the substrate
polarization reversal on the film resistance is realized by utilizing the in-situ and dynamic regulation and control of the
carrier concentration in the film by the surface charge generated by the polarization of the ferroelectric single crystal, and a
novel functional ferroelectric field effect heterostructure which can be obviously regulated and controlled by an electric field
is obtained and shows excellent ferroelectric field effect characteristics. Meanwhile, the invention uses pure-phase titanium
dioxide film TiO with oxygen defect2-Compared with the oxide semiconductor film doped with transition metal ions, the
preparation process and the preparation conditions are effectively simplified for the channel, the adverse factors such as
uneven film components are avoided, and the cost is saved for further application of the ferroelectric field effect
heterostructure.
DRAWINGS DESCRIPTION
FIG. 1 shows TiO prepared in an example of the present invention2-/0.71Pb(Mg1/3Nb2/3)O3-0.29PbTiO3(hereinafter
abbreviated as PMN-29PT) semiconductor ferroelectric field effect heterostructure diagram;
FIG. 2 shows TiO prepared in an example of the present invention2-The structure representation result of the/PMN-29 PT
semiconductor ferroelectric field effect heterostructure;
FIG. 3 shows TiO prepared in an example of the present invention2-The resistance-temperature (R-T) curve graphs of
the/PMN-29 PT semiconductor ferroelectric field effect heterostructure are respectively in positive and negative polarization
states of the single crystal substrate, wherein the insets are the change curves of the film carrier concentration along with
the temperature in the two polarization states;
FIG. 4 shows TiO prepared in an example of the present invention2-A graph of the relative change value of the resistance
of the/PMN-29 PT semiconductor ferroelectric field effect heterostructure under the action of a pulse electric field and time
(delta R/R-T).
INVENTION MODE
Detailed Description
The present invention is further described below in conjunction with the following embodiments and the accompanying
drawings, it being understood that the drawings and the following embodiments are illustrative of the invention only and are
not limiting.
The semiconductor ferroelectric field effect heterostructure based on the lead magnesium niobate titanate single crystal
comprises a substrate (grid) taking the lead magnesium niobate titanate ferroelectric single crystal as a substrate, a
channel (conductive channel) taking a titanium dioxide semiconductor thin film formed on the substrate and gold electrodes
(or silver electrodes or other electrodes) respectively distributed on one side of the lead magnesium niobate titanate single
crystal substrate and one side of the titanium dioxide semiconductor thin film in an evaporation mode or other modes.
Wherein, the thickness of the lead magnesium niobate titanate ferroelectric single crystal substrate can be 0.05-1 mm.
Referring to FIG. 1, TiO prepared in the examples of the present invention2-/0.71Pb(Mg1/3Nb2/3)O3-
0.29PbTiO3(hereinafter abbreviated as PMN-29PT) semiconductor ferroelectric field effect heterostructure schematic. FIG.
1 shows PMN-PT as grid, TiO2-The membrane is a channel. PMN-29The back of PT is coated with gold electrode by
evaporation, and is connected with grid lead; TiO 22-The film gold-evaporated electrode is respectively connected with the
source electrode lead and the drain electrode lead. Wherein the arrows indicate the direction of polarization, which is
defined herein as pointing towards the TiO2-The film is positively polarized, and the pointing PMN-PT back electrode is
negatively polarized.
The chemical formula of the lead magnesium niobate titanate single crystal can be (1-x) Pb (Mg)1/3Nb2/3)O3-
xPbTiO3Wherein x is more than or equal to 0.28 and less than or equal to 0.35, wherein the orientation of the lead
magnesium niobate titanate single crystal can be (001), (110) or (111), and is preferably (001). The film grown using the
(001) -oriented single crystal is optimal in the crystalline and epitaxial properties under the same production conditions.
The chemical general formula of the titanium dioxide semiconductor film is TiO2-Wherein 0. ltoreq. 0.2, preferably 0. ltoreq.
0.1. Titanium dioxide is taken as a typical wide bandgap semiconductor material, TiO grown in an oxygen-deficient
environment and with a bulk in an insulating state2-(0-0.1) oxygen vacancy exists in the film with a certain concentration,
so that the carrier concentration is 1018-1020/cm3In the range of and Ti4+The ion can obtain an electron valence of
Ti3+The ions have ferromagnetism. Thus the corresponding TiO2-the/PMN-PT heterostructure can show remarkable
ferroelectric field effect, and TiO2-Our experiments show that the carrier concentration of titanium dioxide semiconductor
film grown on PMN-PT ferroelectric single crystal substrate is about 1-8 × 1018/cm3Built TiO2-The interface coupling
mechanism of the/PMN-PT heterostructure is mainly a ferroelectric field effect. Wherein the thickness of the titanium
dioxide semiconductor film can be 10-500 nm.
According to the invention, the titanium dioxide semiconductor film is directly grown on the lead magnesium niobate titanate
ferroelectric single crystal substrate, so that the preparation process is simplified, and good interface quality and higher
working efficiency are obtained. Because the lead magnesium niobate titanate ferroelectric single crystal has excellent
ferroelectric performance, the ferroelectric polarization induced by the bias electric field enables the surface of the
ferroelectric single crystal to generate positive or negative charges, thereby inducing the change of the carrier
concentration of the titanium dioxide film, and further enabling the channel resistance of the film to be obviously changed,
and further obtaining a novel functional ferroelectric field effect heterostructure with obvious electric field adjustable
characteristic. The preparation method of the semiconductor ferroelectric field effect heterostructure based on lead
magnesium niobate titanate single crystal provided by the invention is exemplarily illustrated below.
In the invention, TiO is used2The ceramic block is used as a target material, and the pulsed laser deposition technology is
adopted to deposit on a lead magnesium niobate lead titanate single crystal substrate to obtain TiO2-A semiconductor thin
film. Wherein, the film is TiO2-The mid-oxygen deficiency results from a lower oxygen pressure of the deposit, and thus the
TiO can be adjusted by controlling the oxygen pressure of the deposit2-The oxygen vacancy concentration of the
semiconductor film changes the carrier concentration and the conductivity of the semiconductor film.
The process parameters of the pulsed laser deposition technology include, but are not limited to, firstly evacuating the
cavity of the pulsed laser deposition system to < 5 × 10-4Pa, heating the single crystal substrate to 400-600 ℃ as a
deposition temperature, wherein the deposition oxygen pressure is 0.01-15Pa, and controlling the thickness of the film by
controlling the deposition time, wherein the deposition time is usually 10-60 minutes, the laser energy density is 1-
5J/square centimeter, the laser frequency is 1-5Hz, and the distance between the single crystal substrate and the target is
4-7 cm.
Wherein, the purity of the oxygen used in the film deposition is more than or equal to 99.999 percent, the heating rate of the
heating substrate can be 1-10 ℃/min, and after the deposition is finished, the titanium dioxide semiconductor film is cooled
to the room temperature in situ, and the cooling rate can be 1-10 ℃/min.
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.
INVENTION MODE
Example TiO2-/0.71Pb(Mg1/3Nb2/3)O3-0.29PbTiO3(PMN-29 PT for short) preparation of semiconductor ferroelectric field
effect heterostructure, in which PMN-29PT is oriented in (001).
Preparing a film: high purity TiO2The ceramic block is used as a target material, pulse laser deposition is carried out on a
PMN-29PT single crystal substrate with a polished single surface, and the TiO is obtained2-The PMN-29PT semiconductor
ferroelectric field effect heterostructure is prepared by placing a single-side polished (001) oriented PMN-29PT single
crystal substrate into a reaction chamber of a pulsed laser deposition system, and vacuumizing the background of the
reaction chamber to less than 5 × 10-4Pa, and heating the substrate to 600 deg.C, and evacuating the reaction chamber to
less than 5 × 10-4Pa, and filling oxygen gas until the deposition oxygen pressure is 0.5Pa, the laser energy is 3J/square
centimeter, the laser frequency is 5Hz, the distance between the substrate and the target material is 5 centimeters, and the
deposition time is 20 minutes to obtain the TiO2-The film thickness was 148 nm.
The high purity TiO2The purity of the ceramic target is more than 99.99 percent, and the relative density is more than 97
percent.
The purity of the deposited oxygen is more than 99.999 percent, the influence of impurities brought by the environment can
be minimized by adopting high-purity oxygen, and the quality of the prepared film is improved.
The heating rate of the substrate is 1-10 deg.C/min.
After the deposition is finished, the prepared TiO2-the/PMN-29 PT semiconductor ferroelectric field effect heterostructure is
cooled to room temperature in situ at the cooling rate of 1-10 ℃/min.
Preparing an electrode: using PMN-29PT monocrystal substrate as grid electrode, evaporating gold-plated electrode on
back surface of substrate, connecting grid electrode lead and using TiO2-A schematic diagram of a semiconductor
ferroelectric field effect heterostructure constructed with a thin film as a channel, a gold thin film as a source and a drain
deposited as a source and a drain lead respectively, is shown in FIG. 1, wherein the arrows indicate the polarization
direction, which is defined herein to point at TiO2-The film is positively polarized, and the pointing PMN-PT back electrode
is negatively polarized. Wherein the PMN-29PT single crystal substrate is oriented to (001); thickness of the substrate:
0.5mm, and 5mm in length and width; TiO 22-Film thickness: 148nm, gold electrode thickness: 100 nm.
Structural characterization: the following tests were performed on the prepared semiconductor ferroelectric field effect
heterostructure, and the results are shown in fig. 2: FIG. 2 shows TiO prepared in an example of the present invention2-
The structure characterization result of the/PMN-29 PT semiconductor ferroelectric field effect heterostructure. Fig. 2(a) is
an X-ray diffraction (XRD) pattern measured at room temperature, and it can be found that PMN-29PT (00l) (l ═ 1,2,3) and
TiO are excluded2-(00l) (l ═ 4,8) no other peaks appeared, indicating that the film was monophasic and grown with c-axis
orientation.
FIGS. 2(b) and 2(c) are each TiO2-Phi scan of the thin film and PMN-29PT single crystal substrate (101) plane, showing
TiO2-The thin film is epitaxially grown on a PMN-29PT single crystal substrate.
Characterization of electrotransport properties: FIG. 3 shows TiO prepared in an example of the present invention2-The
resistance-temperature (R-T) curve graph of the film of the/PMN-29 PT semiconductor ferroelectric field effect
heterostructure is obtained when the single crystal substrate is in a positive polarization state and a negative polarization
state, wherein the insets are the change curves of the carrier concentration of the film with the temperature of the substrate
in the positive polarization state and the negative polarization state respectively. From fig. 3, it can be seen that, in the
temperature range measured, the sheet resistance of the substrate in the negative polarization state is greater than that of
the substrate in the positive polarization state, and accordingly, the carrier concentration of the former is significantly lower
than that of the latter, indicating that the TiO is present2-the/PMN-29 PT semiconductor ferroelectric field effect
heterostructure realizes obvious regulation and control of an external bias electric field on channel resistance and realizes
different resistance states of the film when the substrate is in different polarization states.
FIG. 4 shows a temperature of 3TiO prepared in the examples of the invention at 00K2-Resistance-time curve diagram
of/PMN-29 PT semiconductor ferroelectric field effect heterostructure under action of positive and negative pulse electric
field. It can be seen from FIG. 4 that the application of positive and negative pulse electric fields can respectively obtain two
resistance states of "on" and "off", indicating that the application of an external bias electric field can realize the application
of the TiO2-Reversible and non-volatile regulation and control of channel resistance of the/PMN-29 PT semiconductor
ferroelectric field effect heterostructure.
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