JP2001322814A - P-type oxide semiconductor and its manufacturing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a p-type oxide semiconductor of group II to V useful as a light emitting element or a light receiving element material or a photocatalyst and to provide a method for manufacturing the p-type oxide semiconductor. SOLUTION: The p-type oxide semiconductor consists of oxide of group X(=II, III, IV, V) and metal-nitrogen bond composed of at least one among group Y(<=X) nitrides, for instance, Li-N, Be-N, Mg-N, Al-N, Ga-N is introduced into the p-type oxide semiconductor.

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to light emission in the ultraviolet region.
P-type oxide that realizes elements, optical sensors, photocatalysts, etc.
The present invention relates to a semiconductor and a manufacturing method thereof. [0002] 2. Description of the Related Art An oxide semiconductor having a large band gap is
In_TwoO_Three, ZnO, SnO_TwoWidely used as transparent electrode like
Have been. Among them, ZnO is the light between the valence band and the conduction band.
Light-emitting and light-receiving elements in the ultraviolet region due to direct transition
It has attracted attention as a material. However, in ZnO, usually n-type half
Because only conductors can be obtained, its application is limited
Had become. Also, TiO_TwoIs widely used as a photocatalyst
Have been. But at low light intensities the quantum efficiency of the photocatalytic reaction
Is high, but quantum efficiency is remarkable at relatively high light intensity.
Low. This is TiO_TwoDoes not generate a p-type semiconductor, so pn junction
Is not formed. [0003] In some cases, an oxide semiconductor exhibits p-type. example
Ba Cu_TwoO and NiO are typical substances. On green NiO
Produce black, low-resistance p-type by adding Li
be able to. However, it is easy to make NiO n-type.
There is no. On the other hand, copper oxide is a superconductor La_2-xSr_xCuO_FourIs p
Type, Nd_2-xCe_xCuO_FourIs known to be of type n,
The band gap is small and black. Thus, less than 3 eV
For oxides with the above band gap and transparent in the visible region,
 No material exhibiting both n-type and p-type conduction has been obtained. Therefore, a p-type oxide semiconductor was manufactured.
Many efforts have been made. Among them, ZnO is vigorous
Has been considered. First, add Li, a Group I (a) element
Was the way. Electric resistance increases up to 0.5% Li content
However, it does not reach the p-type.
 On the other hand, the resistance was reduced in the n-type. This is
Is interpreted as follows. When Li is added to ZnO, Zn²⁺Sa
Li with lattice replacement ⁺Excessive negative charge near ions
, And the electrostatic attraction with lattice oxygen decreases. The result
Vacancy with lattice oxygen deficiency V_oLive near Li
It is easier to achieve. This V_oIs V_o ^2-Like two electrons
Li-V_oThe pair ultimately becomes a donor
Get to work. Thus, Li doping of ZnO is p-type
Was not effective in obtaining [0005] Therefore, Zn²⁺O instead of cation^2-Shade of
Attempts have been made to replace ions with group V elements, such as N.
Was. Even in the initial theoretical calculations, N added to ZnO
Form a sceptor level, low-resistance p-type ZnO doped with nitrogen
It was expected to be realized by. Therefore, ZnO
Radioactivity during N ion implantation and ZnO thin film preparation
Attempts have been made to add N to ZnO by introducing
Was. However, it is not possible to produce p-type ZnO
Was. First, the solubility and solid solubility of N in ZnO
Second, unlike the theoretical prediction, the energy of N in ZnO is
The energy level is much higher than the valence band of the oxide.
(Deep acceptor level). [0006] The first is to increase the concentration of solid solution of nitrogen in ZnO.
In preparing ZnO thin film, excess metal Zn_ThreeReact with
Attempts to introduce high concentrations of Zn-N bonds
As a result, the hole concentration is 1.5 × 10¹⁶cm^-3With a resistivity of 34Ωcm
 Masanobu Kasuga of the University of Yamanashi reported that p-type ZnO was obtained.
(Japan.J.Appl.Phys. Vol.36 (1997) pp.L1453-L145
Five). However, unfortunately, no one followed up on the experiment.
It has not worked. [0007] Tetsuya Yamamoto of Kochi University of Technology and Yoshi of Osaka University
Mr. Tahiro said that by increasing the amount of N
Mitigates the reduced Madelung potential
Group III elements (Al, Ga, In) and N to ZnO
A method of sometimes adding was theoretically proposed. But shallow de
Group III element (M: Al, Ga, In)
In order to obtain p-type conduction by adding N, the amount of N
M needs to be added in a larger amount than element (Al, Ga, In).
N = 1: 1 using a III-V compound with a stoichiometric composition
Question from an experimental point of view
There is a title. Very recently, Kawai et al. Of Osaka University reported that ZnO and Ga
_TwoO_ThreeIs evaporated by laser ablation and this thin film deposition
N in the process_TwoCyclotron resonance plasma in O gas
, ZnO + Ga_TwoO_ThreeIs partially nitrided to a resistivity of several Ωcm,
10 as concentration¹⁹cm^-3Reported that p-type ZnO with
(Japan.J.Appl.Phys. Vol.36 (1999), 11A, pp.L1205
-L1207). Kawai et al. Calculated the ratio of Ga to N from XPS data.
Report 1: 2. But Ga_TwoO_ThreeThe amount of
0.1, 0.5, 5, 10%
Only p-type, N_TwoO pressure is 10 × 10^-15 x 10 from Pa
^-1Carrier number 2 × 10 just by halving Pa and 1/2¹⁹  cm^-3of
 From p-type, 2 × 10¹⁸cm^-3Inverting to n-type
Ga to be added_TwoO_ThreeCorrelation between amount of carrier and carrier concentration
The range of the experimental conditions is extremely narrow,
It is limited to the enclosure. This is the III-V
Presence of donor group III gains p-type in co-doping
This is because it is not preferable. [0009] SUMMARY OF THE INVENTION It is an object of the present invention to provide a light emitting device.
Group II useful as a device or photodetector material or photocatalyst
Provides p-type oxide semiconductors of Group V
 To provide a method for manufacturing a p-type oxide semiconductor
is there. [0010] Means for Solving the Problems To achieve the above object,
For example, a p-type oxide semiconductor comprising a Group II oxide,
Group I nitride or Group II nitride in the p-type oxide semiconductor
Having a metal-nitrogen bond consisting of at least one of
Shall decide. The group II oxide semiconductor is Zn_1-xyBe_xMg
_yO (where 1-x-y> 0, 0 ≦ x ≦ 1, 0 ≦ y ≦ 1)
And good. The Group I nitride is Li_ThreeN;
The monster is Be_ThreeN_TwoOr Mg_ThreeN_TwoShould be at least one of
No. A p-type oxide semiconductor comprising a group III oxide,
Some of the p-type oxide semiconductors include Group I nitrides and Group II nitrides.
Or a metal consisting of at least one of the group III nitrides
-It has a nitrogen bond. The Group III oxide semiconductor is In_TwoO_ThreeIs
good. The group I nitride is Li_ThreeN, and the group II nitride is
Be_ThreeN_TwoOr Mg_ThreeN_TwoAt least one of the group III
The oxide is preferably at least one of AlN or GaN.
A p-type oxide semiconductor comprising a Group IV oxide, wherein
Group oxides, group II nitrides, group III nitrides
Made of at least one of a nitride or a group IV nitride
Metal-nitrogen bond. The Group IV oxide semiconductor is Sn_1-xTi_xO (however
However, it is preferable that 0 ≦ x ≦ 1). The group I nitride is Li_ThreeN
Wherein the group II nitride is Be_ThreeN_TwoOr Mg_ThreeN_TwoLess of
And the group III nitride is AlN or GaN.
At least one, and the group IV nitride is Si_ThreeN_Fourso
Good to be. A p-type oxide semiconductor comprising a group V oxide
Thus, the p-type oxide semiconductor contains a group I nitride and a group II nitride.
At least one of the nitride, group III nitride or group IV nitride
Also have one metal-nitrogen bond. The V-group oxide semiconductor is Nb_{2 (1-X)}Ta_XO
_Five(However, it is preferable that 0 ≦ x ≦ 1). The group I nitride
Is Li_ThreeN, and the group II nitride is Be_ThreeN_TwoOr Mg_ThreeN_Twoof
At least one, wherein the group III nitride is AlN or
At least one of GaN and the group IV nitride is Si
_ThreeN_FourIt is good. P-type oxidation consisting of the above group II oxides
In the method for manufacturing an oxide semiconductor, the group II oxide semiconductor
 Add at least one of Group I nitride or Group II nitride
Shall decide. A p-type oxide half comprising the above group III oxide
In the method for manufacturing a conductor, the group III oxide semiconductor
Group nitrides, group II nitrides, and group III nitrides
Also one is added. From the above group IV oxides
In the method for producing a p-type oxide semiconductor,
Group nitrides, group II nitrides, group III nitrides
Means that at least one group IV nitride is added. A p-type oxide semiconductor comprising the above-described group V oxide
In the method for manufacturing a body, the group V oxide semiconductor is
Oxides, Group II nitrides, Group III nitrides, and Group IV nitrides
Both are to be added. The p-type oxide semiconductor
The manufacturing method of the oxide semiconductor and the nitride
Using nitrogen gas as a target
Therefore, it is preferable to deposit both at the same time. In the method for manufacturing a p-type oxide semiconductor,
And resistance heating the oxide semiconductor and the nitride.
Or evaporate by electron beam heating to deposit both at the same time.
Good to be. In the method for manufacturing a p-type oxide semiconductor,
Laser abrasion of the oxide semiconductor and the nitride
And deposit both at the same time. In the method for manufacturing a p-type oxide semiconductor,
To form while nitriding the component metal of the nitride.
Deposited nitride simultaneously with the oxide semiconductor.
Is preferably added to the oxide semiconductor. The p-type oxidation
In the method for manufacturing a nitride semiconductor, the component metal of the nitride is
By reactive sputtering in nitrogen plasma
It is preferable to add a nitride to the oxide semiconductor. In the method for manufacturing a p-type oxide semiconductor,
The reactive metal of the nitride is reactively vaporized in a nitrogen plasma.
By adding nitride to the oxide semiconductor
And good. In the method for manufacturing a p-type oxide semiconductor,
Laser abrasion of nitride component metal in nitrogen plasma
Addition of nitride to the oxide semiconductor
Good. The present invention is based on the following theoretical theory of the inventors.
Based on prediction. Doping the oxide with nitrogen and p-type
Oxidation has already been pointed out
Not only is the concentration of nitrogen dissolved in the material low,
There is a problem with the energy level of nitrogen in oxides
The inventors thought that it might be. Value for many oxides
The electronic band is composed of 2p orbitals of oxygen O 2, and the conduction band is
Orbitals are the main component (of course, the covalent bond of the metal-oxygen bond)
Naturally, each other's orbits are mixed due to compatibility.) example
For example, in ZnO, the conduction band is mainly composed of Zn 4s and 4p orbitals.
The subassembly consists of O 2p orbitals. Similarly TiO_TwoThen conduction
The band consists of 3d orbitals of Ti and the valence band consists of 2p orbitals of O.
ing. Oxygen has a very high electronegativity in oxides
Since the valence band is formed, the energy level of the valence band
The position is very deep. Doped N is effective
The level of N becomes deep enough to work as a scepter
It is necessary to be. For a quantitative discussion, the nitrogen in ZnO
Energy level is determined by the DV-Xα method (Discrete Varational-X
calculation using the α method or the variable separation local density approximation method).
I tried. As a result, N added to ZnO forms a Zn-N bond.
And the energy level of Zn-N is lower than the valence band of ZnO.
At about 1 eV higher than
It was theoretically shown. Various metal-nitrogen (M-N) bonds to ZnO
The energy level formed when the
When calculated with DV-Xα, Li-N, Be-N, Mg-N, Al-N, Ga
-N has a strong metal-nitrogen bond, and the level of N is
It turned out that it approaches the valence band of the oxide. Oxidation of p-type by introducing strong metal-nitrogen bond
In order to obtain an oxide semiconductor, the metal used is an oxide semiconductor.
It is natural that they do not work as donors in the body.
You. Thus, the present invention provides a method for Ga
And N 2 co-doping is completely different. [0023] BEST MODE FOR CARRYING OUT THE INVENTION (1) p-type with Be-N bond introduced
The preparation of ZnO can be performed as follows. Reactivity
ZnO thin film doped with Be-N bond by sputtering method
Was prepared. Targeting ZnO (99.999%) powder
Used. Part of the surface was previously nitrided on this ZnO powder.
(99.9%) Be metal sheet (5 mm x 5 mm x 0.2
5 mm). Addition to ZnO depending on the number of Be metal sheets
The amount was controlled. 4x chamber for sputtering equipment
Ten^-FourExhaust to Pa, then introduce high-purity nitrogen gas
Sputtering was performed at a force of 1.3 Pa. Sapphire on the substrate
A (α-Al_TwoO_Three) C-plane was used. Substrate temperature from 200 ° C to 30
The test was performed in the range of 0 ° C. RF power ranges from 50W to 150W
I went in. Carriers are holes (p-type) or electrons (n-type)
It is determined by the Seebeck effect and the Hall effect
Was. Analysis of crystal structure of thin film by X-ray diffraction (Cukα)
Was. X-ray photoelectron spectroscopy for elemental analysis in thin films
Method (XPS) and SIMS (secondary ion mass spectrometry)
Was. (2) Preparation of p-type ZnO into which Mg-N bond has been introduced
Can be performed as follows. (2.1) Mg to ZnO (99.999%) powder_ThreeN_Two20% powder
Used a powder mixed with 10% as a target. Spatter
4 x 10^-Four Exhaust to Pa
Then introduce high-purity nitrogen gas and sputter at a pressure of 1.3 Pa.
The ring went. Sapphire (α-Al_TwoO_Three) C-plane
Was used. Substrate temperature should be between 200 ° C and 250 ° C
Was. The high frequency power was set in the range of 50W to 100W. Carry
Seebe is whether the electrons are holes (p-type) or electrons (n-type).
And Hall effect. X-ray diffraction (Cuk
α) was used to analyze the crystal structure of the thin film. Included in thin film
Elemental analysis is X-ray photoelectron spectroscopy (XPS), SIMS
(Secondary ion mass spectrometry). (2.2) Two independent ZnO targets and Mg
_ThreeN_TwoA thin film was formed using a target. Spatter
Ring device chamber 5 × 10^-FourExhaust to Pa
Then introduce high-purity nitrogen gas and sputter at 7 Pa
Was done. Sapphire (α-Al_TwoO_Three) Using c-plane
Was. The substrate temperature was in the range of 200 ° C. to 250 ° C. Cap
Seebe is whether the rear is a hole (p-type) or an electron (n-type).
Judgment based on the lock effect. By X-ray diffraction (Cukα)
The crystal structure analysis of the thin film was performed. (3) Production of p-type ZnO by introduction of Li-N bond
The production can be performed as follows. Li metal sheet
(The shape is 10 mm × 10 mm × 0.25 mm) in nitrogen plasma
(1.3Pa) and the surface is Li_ThreeN. This surface
Li sheet was put on ZnO (99.999%) powder
Targeted things. Depending on the number of this sheet, Li_ThreeN
The amount added to ZnO was controlled. Cha of sputtering equipment
4 × 10^-Four And then purge to high purity nitrogen gas.
And sputtering was performed at a pressure of 1.3 Pa. Base
Quartz glass or sapphire (α-Al_TwoO_Three) C-plane
Was used. Substrate temperature should be between 200 ° C and 500 ° C
Was. High frequency power was applied in the range of 50W to 150W. Carry
Seebe is whether the electrons are holes (p-type) or electrons (n-type).
And Hall effect. X-ray diffraction (Cuk
α) was used to analyze the crystal structure of the thin film. Included in thin film
Elemental analysis is X-ray photoelectron spectroscopy (XPS), SIMS
(Secondary ion mass spectrometry). (4) Preparation of p-type oxide semiconductor other than ZnO P-type oxidation by addition of nitride to the above-mentioned oxide semiconductor
The method of manufacturing a semiconductor is not limited to ZnO,
Zn with Zn site replaced by Be or Mg_1-xBe_xO and Zn
_1-xMg_xGroup II oxide semiconductors (however, 0 ≤ X ≤ 1)
And group III oxide semiconductor In_TwoO_Three, Group IV oxide semiconductor
SnO is the body_Two, TiO_TwoNb which is a group V oxide semiconductor_TwoO_Five,
Ta_TwoO_FiveAlso applicable to At this time, Zn_1-xBe_xO and Zn_1-xMg_xO
(Where 0 ≦ X ≦ 1) such as Zn
Like O, nitride is Li_ThreeN, Be_ThreeN_Two, Mg_ThreeN_TwoIs valid
You. Group III oxide semiconductor In_TwoO_ThreeThen, the nitride is Li_Three
N, Be_ThreeN_Two, Mg_ThreeN_TwoIn addition to the group III nitrides AlN and G
aN can be added. When adding AlN or GaN
Can use these sintered bodies as targets.
Wear. Further, Sn, which is a group IV oxide semiconductor,_1-xTi_x
O_Two(However, 0 ≦ x ≦ 1), Nb which is a group V oxide semiconductor
_{2 (1-X)}Ta_XO_Five(However, when 0 ≦ x ≦ 1), nitride
Is Li_ThreeN, Be_ThreeN_Two, Mg_ThreeN_Two, AlN, GaN, and Group IV nitriding
Si that is an object_ThreeN_FourCan also be added. Si_ThreeN_FourWhen adding
Then, Si_ThreeN_FourAre targets for either powder or sintered
Can be used as Hereinafter, the book
The invention will be described in detail. Example 1 ZnO was doped with Be-N bonds. Be gold whose surface has been previously nitrided on ZnO powder
Be-N on ZnO, targeting on the metal sheet
An attempt was made to dope the bond. Be metal sheet is 50mm long and 50m wide
m, 2.5mm thickness divided into 1/2, 1/4, 1/8
Was. After the thin film is formed, oxygen defects generated in the ZnO target
Remove the Be sheet to reduce
Plasma oxidation treatment was performed at 1.3 Pa and 150 W for 2 hours. ZnO causes oxygen deficiency during sputtering.
Easy to make. That is, some acid on the ZnO target surface
Element is present and this small amount of oxygen inhibits the nitridation of Be metal
BeO may be formed. Therefore, Be metal
On the surface of ZnO powder to check whether
Be metal 1/2 sheet (length 12.5mm x width 25mm x thickness 2.5mm)
Thin film deposition was performed at 150 W on four sheets. Complete deposited ZnO
The substrate temperature was set to 500 ° C. for complete sublimation. Deposited
Thin film deposited from XR (X-ray diffraction) _ThreeN_TwoIn
Turned out to be. Therefore, emission from ZnO powder target
The generated oxygen has a significant effect on the doping of the Be-N bond.
Turned out not to be. In such a manufacturing method, the characteristics of ZnO
The dependence of the RF output was investigated. Zn at 70W, 100W, 120W, 150W
O Be1 / 8 sheet whose surface has been pre-nitrided
2.5mm, width 6.25mm, thickness 2.5mm) 8 or 7
Then, thin films (samples B10, B11, B23, B12) were prepared.
Figure 1 shows the XRD spectrum of the p-type oxide semiconductor according to the present invention.
(A) is B10, (b) is B11, (c) B23, (d) is B1
2 X-ray diffraction intensity is 50Kcps, 100kcps, 50kcp
s, 10kcps. Thin film prepared with 70W RF power (B10)
In the XRD, the sapphire (0,0,0,6) reflection of the substrate is 2θ = 41.
Appears at 72 ° and ZnO (0,0,0,2) reflection is observed at 2θ = 34.4 °
Can be C-axis length estimated from ZnO (0,0,0,2) reflection is 0.51
It is estimated to be nm. In the thin film (B11) produced with an RF output of 100 W, Zn
O (0,0,0,2) reflection is observed at 2θ = 34.76, and c-axis length is
0.51618 nm. Samples B10 and B11 were pure ZnOd
The c-axis length is slightly shorter than 0.5206 nm. 120W
The reflection of ZnO (0,0,0,2) of the thin film prepared in 2 was 2θ = 34.96 °
There is a large shift, and the c-axis length is 0.51324 nm. Be
Since the bond distance of -N is shorter than that of ZnO,
It seems to be ZnO with large addition. With higher RF power of 150W
The XRD of the deposited ZnO thin film shows a peak at 2θ = 35.0 °.
There is a shoulder at θ = 35.5 °. 2θ = 35.0 ° is RF output 120W
It is the same as that produced in Corresponds to 2θ = 35.5
Things are Be, BeO, Be_ThreeN_TwoDoes not match with
It is ZnO with a large amount of Be-N added. The c-axis length of this ZnO is 0.
It is 51026 nm, and the c-axis is considerably shorter. X in Figure 1
From the results of the RD, the Be-N coupling
It turned out that the grouping became remarkable. Samples B10, B11, B23, B12
Tables for anti (measured by two-terminal method) and carrier type
Figure 1 shows. [0035] 【table 1 】 The surface resistances in Table 1 are measured with two platinum terminals.
You. As is clear from Table 1, the resistance value increases with the RF output.
In particular, it decreased dramatically from 700 MΩ to 1 MΩ. Seebeck
The effect is that carriers in each thin film are holes, that is, p-type conductors.
Turned out to be. Next, the powder target was observed and Be_ThreeN_Twoof
We examined whether doping is taking place. RF output 70 described above
When sputtering at W and 100W, ZnO powder
The target had turned black. This has already been mentioned
Oxygen deficiency is generated in ZnO powder. Place
However, after sputtering at 120 W, the powder surface is not
Does not turn black, pale yellow after sputtering at 150 W
Had become. Oxygen deficiency caused by nitrogen ions
Despite the fact that it is not black, (1) Be_ThreeN_TwoIs ZnO
Doped on powder surface, lower Fermi level
Or (2) Be_ThreeN_Two  Oxygen deficiency in ZnO doped with
It was expected that the pits would be less likely to form. Then, a thin film (sample B12) was prepared at 150 W.
After that, continue the oxidation process without
Further, a thin film deposition experiment was performed at 135 W. Deposited thin film (sample
Figure 2 shows the XRD pattern of B13). Weak ZnO for XRD
(0,0,0,2) diffraction peak_ThreeN_TwoDiffraction peak
Was measured. The target remained yellow. As a result
Conducts thin film deposition experiments continuously with RF power of 150W and 135W
And Be simultaneously with sputtering of the ZnO powder surface._ThreeN_TwoIs Zn
O Doped on the powder surface and the effect
Means Therefore, at 135 W or higher, Zn
Be to O_ThreeN_TwoThat the amount of
And suggests. In order to confirm the accumulation effect of this dope, Be
Removed all metal sheets and made a thin film at 150 W
(Sample B8). Target ZnO powder remains pale yellow
Met. When a thin film was further deposited at 70 W (Sample B9)
At that time, the ZnO powder target had turned black. Figure 2 shows
5 is an XRD spectrum of the p-type oxide semiconductor according to the present invention.
(A) is B13, (b) is B8, and (c) is B9. XRD
And ZnO (0,0,0,2) reflection is 2θ = 34.45 °, 2θ = 34.43 °
Was observed. The c-axis length of the obtained ZnO thin film was 0.5207 for B8.
nm and B9 are 0.5201 nm, which almost match the value of pure ZnO.
ing. Table 2 shows the physical properties of the prepared thin films (B13, B8, B9).
Show. [0039] [Table 2]The surface resistance in Table 2 is measured with two platinum terminals.
You. The surface resistance of sample B13 varies from 2 MΩ to 100 MΩ.
So it had changed considerably. This is clear from XRD
This is because the two phases are mixed. 0.2 MΩ for sample B8
It was n-type. This sample was placed at 200 ° C. for 13 hours under 1 atm of oxygen.
Annealing in the atmosphere changes to p-type ZnO with a resistance of 5 MΩ.
(Sample B8). Sample B9 shows a resistance of 20 to 30 MΩ.
It was p-type. This result shows that the surface of the ZnO target
_ThreeN_TwoIs sputtered and sputters at high RF power
A large amount of oxygen vacancies in the deposited ZnO film
And some of the oxygen defects disappear by annealing at relatively low temperature.
 It turns out that it changes to p-type. Oxygen deficiency at weak RF power
Generation of ZnO thin film is p-type immediately after deposition
Turned out to be. Further, a ZnO thin film is formed in a nitrogen atmosphere.
Causes a large amount of oxygen defects in the ZnO powder or thin film.
You. As described above, the larger the RF output, the more oxygen defects occur
Is also remarkable. Therefore, a small amount of oxygen is added to
It was examined whether or not it could be suppressed. Sample B13 contains Zn
O and Be_ThreeN_TwoAnd the target ZnO table
Excess Be on the surface_ThreeN_TwoIs doped. Actual target
The state of G was yellow, not black. Table for this target
The state of the surface is the same as immediately after the preparation of sample B6. Then, the Be metal sheet was removed and the oxygen atmosphere was removed.
The thin film was deposited in an atmosphere of 1.3 Pa (sample B14). This thin
Only ZnO (0002) was observed in the XRD of the film, and the c-axis length was O.
It was 5204 nm, which was the same as the c-axis length of undoped ZnO. Ma
This thin film was an insulator. Three thin film depositions at 120 W
After performing (Samples B25, B26, B27), remove the Be metal sheet.
And 4 × 10^-3Thin film deposition was performed by mixing Pa oxygen. Profit
The thin film (Sample B28) is n-type and has a low resistance of about 30 kΩ
The value was shown. N or Be to ZnO_ThreeN_TwoComplete dope
It can be seen that it is suppressed. Further with the same target
Low concentration 1.3 × 10^-3Thin film deposition by introducing Pa oxygen
As a result, it became an insulator (sample B29). FIG. 3 illustrates the present invention.
It is an XRD spectrum of such a p-type oxide semiconductor, and (a) is
B28 and (b) are B29. Table 3 shows samples B28 and B29
Shows the physical properties of [0043] [Table 3] The result is a small amount of oxygen, i.e. 1.3 x 10^-3Existence of about Pa
Even in the presence of p-type ZnO,
Revealed. This is because nitriding and doping of Be are more important than suppressing oxygen defects.
Means that doping has a dominant effect on p-type ZnO fabrication
are doing. Next, resistance was measured for five representative thin film samples.
The resistance was measured. The resistivity is calculated by the Van der Paw method.
The determination of the carrier was based on the Seebeck effect. these
Table 4 shows the preparation conditions, resistance and resistivity of
You. [0045] [Table 4]FIG. 4 is an XRD spectrum of the p-type oxide semiconductor according to the present invention.
(A) is B22, (b) is B30, and (c) is B36.
However, sample B36 used only ZnO as the target.
Before that, ZnO and Be sheet (1/16
× 16 + 1/8 × 7) and sample B34 with RF output of 150W and 120W
 , B35. Therefore, as described above, ZnO
Be on the target surface_ThreeN_TwoIs doped. Sample B1
In Fig. 3, Be is excessive so that two phases appear._ThreeN_TwoHas been added
However, the resistivity does not drop extremely. In sample B22
The resistivity is very low. The XRD of sample B22 is that of ZnO (0,0,0,2).
And the decrease in c-axis length is hardly observed.
No. Therefore Be to ZnO_ThreeN_TwoIs very small. Trial
From the result of fee B22,_ThreeN_TwoLow resistance by the addition of
 It was confirmed that p-type ZnO could be generated. When the material is a hole conductor due to the Seebeck effect,
The Hall effect was measured for the determined sample B51.
Was. Carrier concentration and holes determined by the Hall effect
Table 5 shows the mobility. Carrier from measurement of Hall effect
Is a hole and is found to be a p-type conductor. [0047] [Table 5] Sample B36 was thinned by X-ray photoelectron spectroscopy (XPS)
Was analyzed. The conditions for preparing the thin film have already been described. Figure
5 is the XPS spectrum of the p-type oxide semiconductor according to the present invention.
Yes, (a) is Zn (2p), (b) is O (1s), (c) Be (1s), (c)
Is N (1s). Thus, Be and N are contained in the ZnO film.
Was confirmed. The binding energy of N is nitrided
And the bond between Zn and Be
It means that it exists. The abundance ratio of each element is Z
It was estimated that n: O: Be: N = 46%: 43%: 3.5%: 7%. N content
Is relatively high at 7%, and the content of Be is relatively low at about 3.5%.
N has almost twice the content of Be,_ThreeN
_TwoIs much higher than the expected N / Be ratio of 2/3.
This is Be_ThreeN_TwoAt the same time as doping in the form of
Is doped in ZnO to form a Zn-N bond.
I taste. Example 2 Synthesis of p-type ZnO with Mg-N bond introduced by the following two methods
I went in. (1) ZnO and Mg_ThreeN_TwoTarget mixed powder
If Target is ZnO (99.999%) powder and Mg_ThreeN_TwoMix the powder
Mixed powder was used. Sputtering equipment chamber
4 x 10^-FourExhaust to Pa, then introduce high purity nitrogen gas
Then, sputtering was performed at a pressure of 1.3 Pa. Substrate on board
Fire (α-Al_TwoO_Three) C-plane was used. RF output, substrate temperature
Degree, ZnO and Mg_ThreeN_TwoThin film production by changing the ratio of
Was. Thin film preparation conditions and physical properties for representative samples
The values are shown in Table 6. [0050] [Table 6]As is evident from Table 6, for samples M1, M4 and M18,
From the Seebeck effect.
 It turned out to be p-type. Between the resistance and the RF output
There is a strong correlation. In other words, when the RF is 70 W,
The resistance is low, and the resistance value is quite high at other RF outputs. FIG. 6 shows the XR of the p-type oxide semiconductor according to the present invention.
D spectrum, where (a) is M1 and (b) is M10. c
Axial length is pure Zn in most samples (except sample M4)
It is slightly longer than O. But that change
Is extremely small. (2) Two independent ZnO and Mg_ThreeN_TwoWhen using a target Two cathodes, a ZnO target (1 inch diameter)
J) and Mg_ThreeN_TwoSpa with target (1 inch diameter)
A thin film was prepared by a cutter. Two targets
The unit was discharged by an independent RF power supply. Mg to ZnO_ThreeN_Two
Doping amount of ZnO target (1 inch diameter) and Mg_ThreeN_Two
Sputtering equipment with target (1 inch diameter)
A thin film was produced by placing it. The two targets are independent
Discharged by RF power supply. Mg to ZnO_ThreeN_TwoDope amount
ZnO target (1 inch diameter) and Mg_ThreeN_Twotarget
(1 inch diameter) controlled by RF power applied.
RF output to ZnO 100W, Mg_ThreeN_TwoWhen the RF output to
  A thin film showing p-type conductivity with MΩ surface resistance (two-terminal method)
Obtained. XRD measurement of this thin film requires ZnO (0,0,0,2) reflection.
And the c-axis length was 0.5215 nm. FIG. 7 shows the XPS spectrum of the sample M1 according to the present invention.
(A) is Zn (2P), (b) is O (1s), and (c) is Mg (2P).
p) and (d) are N (1s). Oxygen O (1s) splits into two
The peak at 531.9 eV is due to OH. Mg is gold
Not by metal but by nitride or oxide,
It is difficult to determine which one. Nitrogen also splits into two
396.47 eV is nitride and 399.33 eV is NH_Two, NO, etc.
are doing. From the XPS measurement results, OH and NH_Two
It turned out that such a molecule exists. This is Zn
O Mg mixed with powder_ThreeN_TwoReacts with water vapor in the atmosphere to produce Mg (O
H)_TwoAnd NH_ThreeBut also the decomposition products together with the spa
And is taken into the thin film. The composition of sample M1 was Zn: O: Mg: N = 37.4%: 47.3%:
It was estimated at 3.8%: 11.5%. Significant nitrogen is present in the sample
And 70% of the nitrogen contained is attributable to nitrides.
Belong to. Therefore, a high concentration of metal-nitrogen bonds in ZnO
Has been introduced. This is the cause of p-type conduction
it is obvious. Example 3 We synthesized p-type ZnO with Li-N bond. On ZnO powder. Li metal plate 3 with nitrided surface
The target was arranged side by side and the thin film (sample L1) shown in Table 7 was
Sputtering was performed under the manufacturing conditions. [0055] [Table 7]FIG. 8 is an XRD spectrum of the p-type oxide semiconductor according to the present invention.
It is. ZnO (1,0, -1,0), ZnO (0,0,0,2), ZnO (1,0, -1,
2) = 31.7 °, 2θ = 34.3 ° and
 It was observed at 2θ = 36.1 °, indicating that it was a polycrystalline ZnO thin film.
Call In this thin film sputtering, the electric resistance immediately after the deposition is
Ten^TenIt was an insulator of Ω or more. 400 ℃, 6 hours, 1 atm
Annealing in oxygen, surface resistance is 0.5 M
Ω, resistivity dropped to 18 Ωcm. P from Seebeck effect
It turned out to be a type conductor. Then, at 400 ° C,
After annealing for 10 hours in 1 atm oxygen,
Ten^TenIt became an insulator of Ω or more. [0057] According to the present invention, X (= II, III, IV)
 , V) a p-type oxide semiconductor comprising a group oxide,
In the p-type oxide semiconductor, Y (≦ X) group nitride
At least one, for example, Li-N, Be-N, Mg-N, Al-N, Ga-N
Have a metal-nitrogen bond consisting of
P-n control of chemically and electrically stable oxide semiconductors
And the following effects are brought about. (1) Group II (a) oxides, for example, ZnO, Zn-Be-
O and Zn-Mg-O both have a band gap of 3 eV or more.
In other words, since the light transition is direct, the light emitting element in the ultraviolet region
It is used as a light receiving element as an element and a light receiving element. light's
As the wavelength becomes shorter, the spatial resolution improves,
Disk), lithography, etc.
Instead of a laser diode. Display with the spread of personal computers
Is used in large quantities, but in addition to the usual CRT
Liquid crystals, organic ELs, etc. are attracting attention. UV light emitting element
Easily create three primary colors by exciting dyes
Can be done. Therefore, a thin and bright display is realized.
come. (2) TiO_TwoIs widely used for photocatalysts
ing. This is TiO_TwoValence electrons generated when is irradiated with light
TiO in the reaction of holes and water in the band_TwoThe dissolution reaction itself progresses
TiO_TwoTo promote the decomposition of organic substances attached to the surface
It is. The efficiency (quantum efficiency) of this decomposition reaction of organic matter is light
Electrons in the conduction band generated by irradiation and holes in the valence band
It is significantly increased by suppressing recombination with OH. Light intensity
When the degree is weak, the quantum efficiency is relatively high. But light irradiation
When the strength is strong, TiO_TwoGenerated inside
Quantum yield decreases rapidly due to disappearing electric field
You. TiO_TwoUsually gives only n-type semiconductors, but p-type TiO
_TwoThus, a pin structure can be introduced.
With this pin structure, the quantum efficiency decreases even under strong light irradiation.
Of solar cells that respond only to ultraviolet light
It becomes possible. TiO for building window glass_TwoMake solar cell
Then, visible light is transmitted as it is, but ultraviolet rays harmful to the human body
Can be shut off and power can be generated at the same time. Eco-friendly power generation
Becomes possible.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 shows an XRD spectrum of a p-type oxide semiconductor according to the present invention, wherein (a) is B10, (b) is B11, (c) B23 is (d)
Is B12. FIG. 2 is an XRD spectrum of a p-type oxide semiconductor according to the present invention, wherein (a) is B13, (b) is B8, and (c) is B9. FIG. 3 is an XRD spectrum of a p-type oxide semiconductor according to the present invention, wherein (a) is B28 and (b) is B29. FIG. 4 is an XRD spectrum of a p-type oxide semiconductor according to the present invention, wherein (a) is B22, (b) is B30, and (c) is B36. 5 is an XPS spectrum of a p-type oxide semiconductor according to the present invention, wherein (a) is Zn (2p), (b) is O (1s), (c) Be (1s),
(c) is N (1s). 6 is an XRD spectrum of a p-type oxide semiconductor according to the present invention, wherein (a) is M1 and (b) is M10. FIG. 7 is an XPS spectrum of Sample M1 according to the present invention,
(a) is Zn (2P), (b) is O (1s), (c) is Mg (2p), (d) is N
(1s). FIG. 8 is an XRD spectrum of a p-type oxide semiconductor according to the present invention.

Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat II (reference) C01G 35/00 C01G 35/00 C 5F049 C23C 14/08 C23C 14/08 K 5F103 14/28 14/28 H01L 21/363 H01L 21/363 31/10 33/00 D 33/00 31/10 A F term (reference) 4G047 AA04 AB01 AC03 AD02 CA01 CB04 CC03 CD02 4G048 AA03 AA04 AB01 AC08 AD02 AE05 4G069 AA08 BA48A BB04A BB04B BB11A BB11B BC10B BC10A BC10B BC11B BC16A BC17A BC18A BC22A BC35A BC35B BC50A BC55A BC56A BD05A CD10 DA05 EA07 FA01 FB02 4K029 AA07 AA09 BA45 BA47 BA49 BA50 BD01 CA01 CA05 CA06 DC05 GA01 5F041 AA11 CA46 CA49 CA57 5F0WA05A02 MB01 MB01 DD01 LL04 NN03 PP19

Claims (1)

Claims 1. A p-type oxide semiconductor comprising a group II oxide, wherein the p-type oxide semiconductor includes a group I nitride or a group II nitride.
A p-type oxide semiconductor having a metal-nitrogen bond made of at least one of group nitrides. 2. The group II oxide semiconductor is Zn _1-xy Be _x Mg _y
2. The p-type oxide semiconductor according to claim 1, wherein O (1-xy> 0, 0 ≦ x ≦ 1, 0 ≦ y ≦ 1) is satisfied. 3. The method according to claim 1, wherein the group I nitride is Li ₃ N, and the group II nitride is at least one of Be ₃ N _{2 and} Mg ₃ N _2. P-type oxide semiconductor. 4. A p-type oxide semiconductor comprising a group III oxide, wherein the p-type oxide semiconductor contains at least one of a group I nitride, a group II nitride or a group III nitride. A p-type oxide semiconductor having a metal-nitrogen bond. 5. The p-type oxide semiconductor according to claim 4, wherein said group III oxide semiconductor is In ₂ O ₃ . 6. The group I nitride is Li ₃ N, and the group II nitride is at least one of Be ₃ N ₂ or Mg ₃ N ₂ ,
The p-type oxide semiconductor according to claim 4, wherein the group II nitride is at least one of AlN and GaN. 7. A p-type oxide semiconductor comprising a group IV oxide, wherein the p-type oxide semiconductor includes a group I nitride, a group II nitride, a group III nitride or a group IV nitride. A p-type oxide semiconductor having a metal-nitrogen bond consisting of at least one of the following. 8. The p-type oxide semiconductor according to claim 7, wherein the group IV oxide semiconductor is Sn _1-x Ti _x O ₂ (where 0 ≦ x ≦ 1). 9. The group I nitride is Li ₃ N, the group II nitride is at least one of Be ₃ N ₂ or Mg ₃ N ₂ and the group III nitride is at least one of AlN or GaN. 9. The p-type oxide semiconductor according to claim 7, wherein the number is one and the group IV nitride is Si ₃ N ₄ . 10. A p-type oxide semiconductor comprising a group V oxide, wherein the p-type oxide semiconductor includes a group I nitride, a group II nitride, a group III nitride, or a group IV nitride. A p-type oxide semiconductor, characterized by having a metal-nitrogen bond comprising at least one of the following. 11. The group V oxide semiconductor is Nb _{2 (1-X)} Ta _X O.
₅ (where 0 ≦ x ≦ 1).
0. The p-type oxide semiconductor according to 0. 12. The group I nitride is Li ₃ N, the group II nitride is at least one of Be ₃ N ₂ or Mg ₃ N ₂ and the group III nitride is at least one of AlN or GaN. 12. The p-type oxide semiconductor according to claim 10, wherein the number is one and the group IV nitride is Si ₃ N ₄ . 13. The method according to claim 13, wherein the group II oxide semiconductor includes a group I nitride or
4. The method for producing a p-type oxide semiconductor according to claim 1, wherein at least one of group II nitrides is added. 14. A group I nitride, a group II nitride, a group II nitride,
7. The method for producing a p-type oxide semiconductor according to claim 4, wherein at least one of a group III nitride and a group III nitride is added. 15. The group IV oxide semiconductor, wherein at least one of a group I nitride, a group II nitride, a group III nitride or a group IV nitride is used.
10. The method for producing a p-type oxide semiconductor according to claim 7, wherein one is added. 16. The semiconductor device according to claim 10, wherein at least one of a group I nitride, a group II nitride, a group III nitride, and a group IV nitride is added to the group V oxide semiconductor. Or a method for producing a p-type oxide semiconductor. 17. The method for manufacturing a p-type oxide semiconductor according to claim 13, wherein the oxide semiconductor and the nitride are simultaneously deposited by sputtering using nitrogen gas as a target. 17. The method for producing a p-type oxide semiconductor according to any one of 16. 18. The method of manufacturing a p-type oxide semiconductor according to claim 13, wherein the oxide semiconductor and the nitride are evaporated by resistance heating or electron beam heating, and both are deposited simultaneously. The method for producing a p-type oxide semiconductor according to any one of the above. 19. The method according to claim 13, wherein in the method of manufacturing a p-type oxide semiconductor, the oxide semiconductor and the nitride are subjected to laser ablation, and both are simultaneously deposited. A method for manufacturing a p-type oxide semiconductor. 20. In the method for manufacturing a p-type oxide semiconductor, the generated nitride is added to the oxide semiconductor by depositing the generated nitride simultaneously with the oxide semiconductor while nitriding the component metal of the nitride. 17. The method for producing a p-type oxide semiconductor according to claim 13, wherein: 21. The method of manufacturing a p-type oxide semiconductor, wherein the nitride is added to the oxide semiconductor by reactively sputtering the component metal of the nitride in a nitrogen plasma. 21. The method for producing a p-type oxide semiconductor according to 20. 22. The method of manufacturing a p-type oxide semiconductor, wherein the nitride is added to the oxide semiconductor by reactively depositing a component metal of the nitride in a nitrogen plasma. 21. The method for producing a p-type oxide semiconductor according to 20. 23. The method of manufacturing a p-type oxide semiconductor according to claim 20, wherein the nitride is added to the oxide semiconductor by laser ablation of the component metal of the nitride in nitrogen plasma. 3. The method for producing a p-type oxide semiconductor according to item 1.