JP5242083B2 - Crystalline oxide semiconductor and thin film transistor using the same - Google Patents

Description

  The present invention relates to a crystalline oxide semiconductor and a thin film transistor using the same.

Field effect transistors are widely used as unit electronic elements, high frequency signal amplifying elements, liquid crystal driving elements and the like of semiconductor memory integrated circuits.
In particular, with the remarkable development of display devices in recent years, thin film transistors are used as switching elements for driving display devices in various display devices such as liquid crystal display devices (LCD), electroluminescence display devices (EL), and field emission displays (FED). (TFT) is used.

  As a material for the transistor, a silicon semiconductor is most widely used because of stability, good workability, and the like. However, in recent years, a transparent semiconductor thin film made of a metal oxide has attracted attention as being more stable than a TFT using a silicon semiconductor.

  For example, various techniques for producing an amorphous transparent semiconductor film made of a metal oxide such as indium oxide, gallium oxide, zinc oxide by a PLD (pulse laser deposition) method and driving a thin film transistor are disclosed ( Patent Documents 1 to 5).

However, for example, a transparent semiconductor thin film obtained using zinc oxide has the disadvantages that the field effect mobility is as low as about 1 cm ² / V · sec, the on-off ratio is small, and leakage current is likely to occur. . Moreover, since the transparent semiconductor film obtained using zinc oxide is amorphous, it has poor chemical resistance, wet etching is difficult, and practical application is difficult.

  In addition, the amorphous transparent semiconductor thin film has a disadvantage that the refractive index is large and the transmittance of the multilayer film is easily lowered, and oxygen, water, etc. in the atmospheric gas are adsorbed to change the electrical characteristics and reduce the yield. Was.

In addition, although an attempt has been made to make an indium oxide film containing no metal other than indium as a semiconductor (Non-patent Document 1), when a transistor is formed, carrier control cannot be performed well, and field effect mobility is low. Sufficient characteristics were not obtained.
JP 2003-86808 A JP 2004-273614 A JP 7-235219 A JP 2006-165528 A JP 2006-165532 A International Publication No. 2006/095733 Pamphlet Journal of Non-Crystaline Solids 352 (2006) 2311

An object of the present invention is to provide a crystalline oxide semiconductor having a low carrier concentration, a high hole mobility, and a large energy band gap.
An object of the present invention is to provide a thin film transistor having improved device characteristics such as heat resistance, chemical resistance, threshold shift amount during long-term use, field effect mobility, on-off ratio, and the like.

According to the present invention, the following crystalline oxide semiconductor and the like are provided.
1. Containing indium and one or more metal elements M;
In the radial distribution function (RDF) obtained by X-ray absorption spectroscopy, the maximum value of RDF with an interatomic distance between 0.3 nm and 0.36 nm is A, and the interatomic distance is between 0.1 nm and 0.2 nm. A crystalline oxide semiconductor that satisfies a relationship of 0.1 <A / B <1, where B is the maximum value of RDF.
2. 2. The crystalline oxide semiconductor according to 1, which does not contain a peak component between a valence band peak caused by oxygen 2p orbit and a peak caused by conduction electrons in X-ray electron spectroscopy (XPS).
3. 3. The crystalline oxide semiconductor according to 1 or 2, which is a polycrystalline oxide exhibiting a bixbyite crystal structure and has an electron carrier concentration of less than 1 × 10 ¹⁸ cm ⁻³ .
4). 4. The crystalline oxide semiconductor according to any one of 1 to 3, having a range in which the electron mobility with respect to the electron carrier concentration increases logarithmically in proportion to the increase in the electron carrier concentration.
5. The crystalline oxide semiconductor according to any one of 1 to 4, wherein an atomic ratio of indium and the metal element M satisfies the following formula.
M / (M + In) = 0.0001 to 0.13
6). The crystalline oxide semiconductor according to any one of 1 to 5, wherein the metal element M is a positive divalent metal element.
7. The crystalline oxide semiconductor according to any one of 1 to 6, wherein the metal element M is Zn.
8). The crystalline oxide semiconductor according to any one of 1 to 7, wherein the content of a positive trivalent or higher metal element having an ionic radius of 0.7 to 0.92% is 4000 ppm or less.
9. A step of forming an amorphous oxide semiconductor film by sputtering on a substrate at 100 ° C. or lower using a target containing indium and at least one metal element M and setting the water pressure in the system to 10 ⁻³ Pa or lower. The manufacturing method of the crystalline oxide semiconductor in any one of 1-8 containing these.
10. The crystalline oxide according to 9, wherein the crystalline oxide semiconductor is produced by heat-treating the amorphous oxide semiconductor at an oxygen partial pressure of 21000 Pa or more in the system and a heating temperature of 250 ° C. or more for 0.1 to 120 minutes. Semiconductor manufacturing method.
11. A thin film transistor using the crystalline oxide semiconductor according to any one of 1 to 8 as an active layer.
12 12. The thin film transistor according to 11, wherein the amorphous oxide semiconductor is used for a source electrode, a drain electrode and a gate electrode.

According to the present invention, a crystalline oxide semiconductor having a low carrier concentration, a high hole mobility, and a large energy band gap can be provided.
According to the present invention, it is possible to provide a thin film transistor having improved device characteristics such as heat resistance, chemical resistance, field effect mobility, and on-off ratio.

The crystalline oxide semiconductor of the present invention contains indium and one or more metal elements M.
The metal element M is a metal element other than indium, and is preferably a positive divalent metal element.
The positive divalent metal element is an element that can take positive divalence as an valence in an ionic state. For example, Zn, Be, Mg, Ca, Sr, Ba, Ti, V, Cr, Mn, Fe, Co, Ni , Pd, Pt, Cu, Ag, Cd, Hg, Sm, Eu, Yb, and the like, preferably Zn, Mg, Mn, Co, Ni, Cu, and Ca.

Of these preferable positive divalent metal elements, Zn, Mg, Cu, Ni, Co and Ca are more preferable from the viewpoint of carrier concentration control, and Cu and Ni are more preferable.
Among these preferable positive divalent metal elements, Zn and Mg are more preferable from the viewpoint of the transmittance and band gap of the semiconductor. In particular, Zn is more preferable because there are few etching residues.

  Examples of the metal element M other than the positive divalent metal element include Sn, Ge, Si, Ti, C, Pb, Zr, Hf, V, Nb, Ta, Mo, W, Mn, Tc, Re, Fe, Ru, Os, Rh, Ir, Pd, Pt, etc. are mentioned. Among these, Sn, Ge, Si, Ti, Zr and Hf are preferable because the carrier concentration can be controlled efficiently.

In the crystalline oxide semiconductor of the present invention, the atomic ratio M / (M + In) of indium and metal element M is preferably 0.0001 to 0.13, more preferably 0.01 to 0.1, and still more preferably. It is 0.03-0.95, Most preferably, it is 0.06-0.9.
When M / (M + In) is less than 0.0001, it is difficult to make the electron carrier concentration of the crystalline oxide semiconductor less than 1 × 10 ⁻¹⁷ / cm ³ , and M / (M + In) exceeds 0.13 There is a possibility that the crystallization temperature during the production of the crystalline oxide semiconductor is increased.

In the crystalline oxide semiconductor of the present invention, the content of a positive trivalent or higher metal element having an ionic radius of 0.7 to 0.92% is preferably 4000 ppm or less.
When the content of the positive trivalent or higher metal element exceeds 4000 ppm, the solid solution of the metal element M in indium may be hindered.

  Examples of the positive trivalent or higher metal element include Sn, Ge, Si, Ti, C, Pb, Zr, Hf, V, Nb, Ta, Mo, W, Mn, Tc, Re, Fe, Ru, Os, Rh, Ir, Pd and Pt are mentioned.

  In addition, the crystalline oxide semiconductor of this invention may contain another component in the range which does not impair the effect of this invention. For example, the crystalline oxide semiconductor of the present invention may contain at least one element selected from Ar, Kr, Xe, Ne, and N. By including these elements, the crystalline oxide semiconductor can easily control the electron carrier concentration.

  In the crystalline oxide semiconductor of the present invention, the maximum value of RDF between the atomic distances of 0.3 nm and 0.36 nm in the radial distribution function (RDF) obtained by X-ray absorption spectroscopy is A, and the interatomic distance Satisfies the relationship of 0.1 <A / B <1, where B is the maximum RDF value between 0.1 nm and 0.2 nm.

The radial distribution function is obtained by measuring an X-ray absorption wide-area fine structure (EXAFS) by X-ray absorption spectroscopy using synchrotron radiation or the like, and Fourier transforming this EXAFS.
In the present invention, by comparing the radial distribution function of the metal element M in the indium oxide crystal and the radial distribution function of indium oxide, the presence or absence of the solid solution of the metal element M in the indium oxide crystal and the solid solution The condition such as degree can be grasped.

  The A / B is preferably 0.15 to 0.8, more preferably 0.2 to 0.6. When A / B is 0.1 or less, there is little solid solution of the metal element M in the indium oxide crystal, and carriers may not be sufficiently controlled (reduced). On the other hand, when A / B is 1 or more, the crystal has strain, and the mobility may decrease due to scattering due to the strain.

The crystalline oxide semiconductor of the present invention preferably does not include a peak component between a valence band peak caused by oxygen 2p orbital and a peak caused by conduction electrons in X-ray electron spectroscopy (XPS).
In the case of forming a metal oxide, an impurity level is often generated between the band gaps. Impurity levels are caused by unstable structural defects, and when exposed to air in the air after film formation, oxygen, moisture, etc. are adsorbed on the surface of the metal oxide film, and a high resistance layer is easily formed. When no peak component is included between the valence band peak due to the oxygen 2p orbit and the peak due to the conduction electron, such a high resistance layer is not formed.

The crystalline oxide semiconductor of the present invention is preferably a polycrystalline oxide exhibiting a bixbite type crystal structure, and has an electron carrier concentration of less than 1 × 10 ¹⁸ cm ⁻³ .
The oxide semiconductor of the present invention can increase hole mobility by taking a bixbyite structure. This is presumed to be due to the fact that the 5S orbital of indium contained in the crystalline oxide semiconductor has a ridge shared structure. In addition, since the crystalline oxide semiconductor of the present invention is a polycrystalline oxide, the crystalline oxide semiconductor can be made large in area and uniform.

In the case where the electron carrier concentration of the crystalline oxide semiconductor of the present invention is 1 × 10 ¹⁸ cm ⁻³ or more, when this crystalline oxide semiconductor is used as an active layer of a thin film transistor, leakage current may increase.

The electron carrier concentration of the crystalline oxide semiconductor of the present invention is preferably 1 × 10 ¹⁶ cm ⁻³ or less. When the electron carrier concentration of the crystalline oxide semiconductor is 1 × 10 ¹⁶ cm ⁻³ , a normally-off TFT can be obtained with high yield. The lower limit of the electron carrier concentration is not particularly limited as long as it can be applied as a TFT channel layer, and is, for example, 10 ¹² cm ⁻³ .

The electron carrier concentration of the crystalline oxide semiconductor can be measured by Hall effect measurement, and preferably by AC Hall measurement.
In the present invention, the electron carrier concentration of the crystalline oxide semiconductor is a value measured at room temperature. The room temperature is, for example, 25 ° C., specifically a temperature appropriately selected from the range of about 0 ° C. to 40 ° C.
Further, the electron carrier concentration of the crystalline oxide semiconductor of the present invention does not have to be less than 1 × 10 ¹⁸ cm ⁻³ in the entire temperature range described above. For example, the electron carrier concentration may be less than 1 × 10 ¹⁸ cm ⁻³ at 25 ° C.

  The crystalline oxide semiconductor of the present invention preferably has a range in which the electron mobility with respect to the electron carrier concentration increases logarithmically in proportion to the increase in the electron carrier concentration. Such a crystalline oxide semiconductor has an electron mobility that increases as the electron carrier concentration increases, so it is easy to increase the on-off ratio, and even if the electron mobility is increased, the off-current is less likely to increase. Semiconductor characteristics can be easily set.

  The crystalline oxide semiconductor of the present invention can be manufactured, for example, by forming an amorphous oxide semiconductor film over a substrate using a target containing indium and one or more metal elements M, and then performing heat treatment.

As a film forming method, a sputtering method such as a DC sputtering method, a DC magnetron sputtering method, an AC sputtering method, an AC magnetron sputtering method, an RF sputtering method, an RF magnetron sputtering method, a counter target sputtering method, a cylindrical target sputtering method, an ECR sputtering method, or the like. , Resistance heating method, electron beam heating method, vacuum deposition method such as pulsed laser deposition (PLD) method, ion plating method such as ARE method and HDPE method, and CVD method such as thermal CVD method and plasma CVD method It is done. Among these film forming methods, the DC magnetron sputtering method and the AC magnetron sputtering method are preferable, and the DC magnetron sputtering method is more preferable because of low cost, stable discharge, and easy enlargement.
As for the sputtering method, co-sputtering, reactive sputtering, and DC / RF superimposed sputtering may be used.

  When the amorphous oxide semiconductor is formed, the substrate temperature is preferably 100 ° C. or lower, more preferably 50 ° C. or lower. When the substrate temperature exceeds 100 ° C., it may be difficult to make the obtained crystalline oxide semiconductor have a low electron carrier concentration and a high electron transfer.

The film formation of the amorphous oxide semiconductor is preferably performed in an atmosphere where the partial pressure of water in the system is 10 ⁻³ Pa or less, more preferably in an atmosphere of 5 × 10 ⁻⁴ Pa or less. When the partial pressure of water in the system exceeds 10 ⁻³ Pa, the solid solution of the metal element M in the indium is hindered, making it difficult to control the carrier, or generating a hydroxyl group in the indium oxide. May occur, and the electron mobility of the obtained crystalline oxide semiconductor may be reduced.

In addition to the above, examples of conditions for forming an amorphous oxide semiconductor include the following.
When the sputtering method is used as the film formation method, the ultimate pressure in the system during film formation is usually 5 × 10 ⁻² Pa or less, preferably 5 × 10 ⁻³ Pa or less, more preferably 5 × 10 ⁻⁴ Pa. Or less, more preferably 1 × 10 ⁻⁴ Pa or less, and most preferably 5 × 10 ⁻⁵ Pa or less.
When the ultimate pressure exceeds 5 × 10 ⁻² Pa, the electron mobility of the obtained crystalline oxide semiconductor may be reduced due to impurities in the system.

The partial pressure of oxygen in the system during film formation is usually 40 × 10 ⁻³ Pa or less. When the oxygen partial pressure in the system exceeds 40 × 10 ⁻³ Pa, the electron mobility of the obtained crystalline oxide semiconductor may be decreased, and the carrier concentration may be unstable. Moreover, there is a possibility that a residue is generated during wet etching.

The distance between the target and the substrate during sputtering (ST distance) is usually 150 mm or less, preferably 110 mm or less, particularly preferably 80 mm or less.
When the ST distance is the above distance, activation of the metal element M can be expected by exposing the substrate to plasma during sputtering. On the other hand, when the ST distance exceeds 150 mm, the film formation rate decreases, which may not be suitable for industrialization.

  The oxygen pressure in the system when heat-treating the formed amorphous oxide semiconductor is preferably 21000 Pa or more, more preferably 24000 Pa or more, and further preferably 27000 Pa or more. When the oxygen pressure in the system is less than 21000 Pa, oxygen vacancies in the crystalline oxide semiconductor increase, so that the solid solution of the metal element M in indium oxide is hindered by the structural change, and carrier control may not be possible.

The heating temperature in the heat treatment is preferably 250 ° C. or higher, more preferably 250 to 700 ° C., further preferably 280 to 650 ° C., particularly preferably 350 to 600 ° C., and most preferably. Is 400-550 degreeC.
When the heating temperature is less than 250 ° C., the solid solution of the metal element M in indium oxide is hindered, and carrier control may not be possible.

  The heat treatment time is preferably 0.1 to 120 minutes, more preferably 0.5 to 30 minutes, and further preferably 1 to 10 minutes. When the heat treatment time is shorter than 0.1 minutes, solid solution of the metal element M in indium oxide is hindered, and carrier control may not be possible. On the other hand, when the heat treatment time exceeds 120 minutes, the metal element M may be separated from indium oxide and may not be easily dissolved in indium oxide, and the substrate may be deformed when applied to a large area.

  The heat treatment method is not particularly limited, and can be performed by a furnace such as an electric furnace or rapid thermal annealing (RTA), for example. RTA is preferably used because the substrate can be heated to a high temperature in a short time without damaging the substrate and the metal element M is easily dissolved in indium oxide. By raising the temperature in a short time, it is presumed that high energy can be given to the atoms, solid solution can be promoted, and the carrier concentration can be easily controlled.

The crystalline oxide semiconductor of the present invention can be suitably used as an active layer of a thin film transistor.
FIG. 1 is a schematic cross-sectional view showing an embodiment of the thin film transistor of the present invention.
In the thin film transistor 1, the gate electrode 20 is sandwiched between the glass substrate 10 and the gate insulating film 30, and a crystalline oxide semiconductor thin film 40 is stacked on the gate insulating film 30 as an active layer. Further, a source electrode 50 and a drain electrode 52 are provided so as to cover the crystalline oxide semiconductor thin film 40.
Although the thin film transistor 1 of FIG. 1 is a bottom gate type, the thin film transistor of the present invention may have various configurations such as a top gate type.

  The crystalline oxide semiconductor thin film 40 is a thin film made of the crystalline oxide semiconductor of the present invention. By using the crystalline oxide semiconductor of the present invention as the active layer, the heat resistance, chemical resistance, field effect mobility, on-off ratio, and the like of the thin film transistor 1 can be improved.

  The thickness of the crystalline oxide semiconductor thin film 40 is usually 0.5 to 500 nm, preferably 1 to 150 nm, more preferably 3 to 80 nm, and particularly preferably 10 to 60 nm. For example, when the thickness of the crystalline oxide semiconductor thin film is 3 to 80 nm, TFT characteristics such as field effect mobility and on-off ratio are good.

  When the thickness of the crystalline oxide semiconductor thin film is less than 0.5 nm, it may be difficult to industrially uniformly form the crystalline oxide semiconductor thin film. On the other hand, when the thickness of the crystalline oxide semiconductor thin film exceeds 500 nm, the film formation time becomes long, which may reduce the production efficiency.

  The ratio W / L of the channel width W and channel length L of the TFT is usually 0.1 to 100, preferably 1 to 20, and particularly preferably 2 to 8. When W / L exceeds 100, the leakage current may increase or the on-off ratio may decrease. On the other hand, when W / L is less than 0.1, the field effect mobility may be lowered, or pinch-off may be unclear.

  The channel length L is usually 0.1 to 1000 μm, preferably 1 to 100 μm, more preferably 2 to 10 μm. When the channel length L is less than 0.1 μm, it is difficult to manufacture industrially, and a short channel effect may appear or a leakage current may increase. On the other hand, when the channel length L exceeds 1000 μm, the element may become too large or the drive voltage may increase.

The gate insulating film 30 is made of, for example, SiO ₂ , SiN _x , SiON, Al ₂ O ₃ , Ta ₂ O ₅ , TiO ₂ , MgO, ZrO ₂ , CeO ₂ , K ₂ O, Li ₂ O, Na ₂ O, Rb. _It consists of oxides such as ₂ O, Sc ₂ O ₃ , Y ₂ O ₃ , Hf ₂ O ₃ , CaHfO ₃ , PbTi ₃ , BaTa ₂ O ₆ , SrTiO ₃ , and AlN.
Of the above oxides, preferably _{SiO 2, SiN x, Al 2} O 3, Y 2 O 3, Hf 2 O 3, CaHfO 3, more preferably _{SiO 2, SiN x, Y 2} O 3, Hf 2 O 3 , CaHfO ₃ , particularly preferably Y ₂ O ₃ .
The number of oxygen in the oxide does not necessarily match the stoichiometric ratio (for example, it may be SiO ₂ or SiO _x ).

  The gate insulating film may have a structure in which two or more different insulating films are stacked. The gate insulating film may be crystalline, polycrystalline, or amorphous, but is preferably polycrystalline or amorphous from the viewpoint of ease of manufacture.

  The gate electrode 20, the source electrode 50, and the drain electrode 52 are preferably made of an amorphous oxide semiconductor. By using an amorphous oxide semiconductor for the gate electrode 20, the source electrode 50, and the drain electrode 52, electrode processing such as wet etching is facilitated, and durability of the thin film transistor 1 can be improved.

  The band gap of the amorphous oxide semiconductor used for the gate electrode 20, the source electrode 50, and the drain electrode 52 is preferably 2.5 eV to 6.5 eV, more preferably 2.8 eV to 5.5 eV. If the band gap is less than 2.5 eV, the transparency of these electrodes may be deteriorated, and if the band gap exceeds 6.5 eV, the conductivity of these electrodes may be reduced.

The amorphous oxide semiconductor used for the gate electrode 20, the source electrode 50, and the drain electrode 52 preferably contains indium and one or more metal elements N.
When the amorphous oxide semiconductor contains indium, high mobility is easily obtained even when the electrode is amorphous. In addition, when the amorphous oxide semiconductor contains the metal element N that is not indium, the amorphous state of the amorphous oxide semiconductor is stabilized, and the electrode can have a uniform and large area.

  The metal element N contained in the amorphous oxide semiconductor is preferably the same as the metal element M contained in the crystalline oxide semiconductor of the present invention constituting the crystalline oxide semiconductor thin film 40. Since the metal element N and the metal element M are the same, the performance change by metal diffusion can be suppressed.

The atomic ratio N / (N + In) of indium and metal element N contained in the amorphous oxide semiconductor is preferably 0.05 to 0.5, more preferably 0.07 to 0.4, and even more preferably. Is 0.1 to 0.35, particularly preferably 0.14 to 0.3.
When the atomic ratio N / (N + In) of indium and metal element N is less than 0.05, the electrode may be crystallized or a residue may remain during wet etching. On the other hand, when the atomic ratio N / (N + In) of indium and the metal element N exceeds 0.5, the resistance of the electrode is increased due to the thermal history, and it may not be used as an electrode.

  The atomic ratio between the metal element M and the metal element N is preferably N / M> 1, and more preferably N / M> 2. When the atomic ratio of the metal element M and the metal element N is in the above range, it is easy to make an electrode that is amorphous and an active layer that is crystalline.

In order to improve the stability of the crystalline oxide semiconductor thin film 40, an etching stopper layer is preferably provided on the crystalline oxide semiconductor thin film 40. As the etching stopper layer, a layer formed of the gate insulating film 30 such as SiN _x or SiO ₂ or an organic insulating film such as polyimide or parylene can be used. The etching stopper layer may be a layer in which an inorganic insulating film and an organic insulating film are stacked and / or mixed.
The thin film transistor 1 preferably further includes a protective film as a whole and is not in direct contact with the atmosphere.
As the protective film, a film made of the same material as the gate insulating film such as SiN _x or SiO ₂ or an organic insulating film such as polyimide or parylene can be used. Further, a protective film in which an inorganic insulating film and an organic insulating film are stacked and / or mixed may be used.

Example 1
(1) Production of sputtering target As raw materials, indium oxide and zinc oxide powder are mixed so that the atomic ratio In / (In + Zn) is 0.93 and the atomic ratio Zn / (In + Zn) is 0.07. The mixed powder was supplied to a wet ball mill and mixed and ground for 72 hours to prepare a raw material fine powder.
The obtained raw material fine powder was granulated and press-molded into dimensions of 10 cm in diameter and 5 mm in thickness to obtain a molded body. This compact was put into a firing furnace and fired at 1450 ° C. for 12 hours to obtain a target (sintered body).

(2) Film formation of amorphous oxide semiconductor thin film The obtained sputtering target was mounted on an RF magnetron sputtering film forming apparatus and sufficiently baked, and then a 350 nm thick film was formed on a glass substrate (Corning 1737). A transparent and polycrystalline amorphous oxide semiconductor thin film was formed. It was confirmed by X-ray crystal structure analysis that the obtained amorphous oxide semiconductor thin film was polycrystalline.

The sputtering conditions are as follows.
Substrate temperature: 25 ° C
Ultimate pressure: 5 × 10 ⁻⁶ Pa
Atmospheric gas: Ar100%
Sputtering pressure (total pressure): 1 × 10 ⁻¹ Pa
Input power: 100W
Deposition time: 60 minutes ST distance: 100 mm
Water pressure: 1 × 10 ⁻⁴ Pa or less (The water pressure was measured using a quadrupole mass spectrometer (Q-mass).)

(3) Crystallization of amorphous oxide semiconductor thin film The obtained amorphous oxide semiconductor thin film was heat-treated at 300 ° C. for 1 hour at an oxygen partial pressure of 35000 Pa (remaining nitrogen and argon). A thin film was prepared.
When this crystalline oxide semiconductor thin film was analyzed by the ICP method, the atomic ratio [In / (In + Zn)] was 0.93, and the atomic ratio [Zn / (In + Zn)] was 0.07.

The obtained crystalline oxide semiconductor thin film was confirmed to be a polycrystalline oxide having a bixbite type crystal structure by X-ray crystal structure analysis. In addition, the manufactured crystalline oxide semiconductor thin film does not include a peak component between a valence band peak caused by oxygen 2p orbit and a peak caused by conduction electrons (band gap) by X-ray electron spectroscopy (XPS). It was confirmed. The energy band gap of the crystalline oxide semiconductor thin film was 3.7 eV, which was confirmed to be sufficiently large.
The band gap measurement conditions are as follows.
Measuring device: ESCA5400 (manufactured by ULVAC-PHI)
X-ray source: Al-Kα
Peak reference: Indium 3d _5/2 set to 445 eV

(4) Evaluation of physical properties The carrier concentration and electron mobility of the obtained crystalline oxide semiconductor thin film were measured using a Hall measuring device (Resi Test 8310, manufactured by Toyo Corporation). As a result, the electron carrier concentration of the crystalline oxide semiconductor thin film was 9 × 10 ¹³ cm ⁻³ . Further, the contents of Li, Na and K by ICP emission analysis were all 1000 ppm or less.

The measurement conditions for the electron carrier concentration and the electron mobility are as follows.
Measurement temperature: Room temperature (25 ° C)
Measurement magnetic field: 0.5T
Measurement current: 10 ⁻¹² to 10 ⁻⁴ A
Measurement mode: AC magnetic field hall measurement

  When the transparency of the obtained crystalline oxide semiconductor thin film was measured using a spectrophotometer, the light transmittance of light having a wavelength of 400 nm was 85%, and it was confirmed that the film had excellent transparency.

Using the sputtering target manufactured in (1), a crystalline oxide semiconductor thin film was formed on a silicon substrate so as to have a film pressure of 500 nm under the same conditions as in (2) and (3), and the obtained crystalline oxidation The radial distribution function (RDF) was determined for the physical semiconductor thin film.
In addition, the measuring method of a radial distribution function is as follows.
X-ray scattering measurement was performed by a grazing incidence X-ray scattering method using an energy X-ray of 20 keV extracted from the radiant light obtained using the synchrotron radiation facility SPring-8, and an X-ray scattering curve was obtained. The scattering curve was Fourier transformed to obtain a radial distribution function.

  The radial distribution function of the crystalline oxide semiconductor thin film manufactured in Example 1 is shown in FIGS. The maximum RDF value between the atomic distances of 0.3 nm to 0.36 nm of the prepared crystalline oxide semiconductor thin film is A, and the maximum RDF value between the atomic distances of 0.1 nm to 0.2 nm is B. In this case, A / B was 0.5.

(5) Evaluation of thin film transistor On the silicon substrate under the same conditions as (2) and (3), using the target manufactured in (1) so that W = 40000 μm and L = 100 μm on the silicon substrate with a thermal oxide film. A thin film 80 nm crystalline oxide semiconductor thin film was formed to produce a thin film transistor. The obtained thin film transistor was evaluated. As a result, the field effect mobility of the obtained thin film transistor is ^6cm 2 / Vs, on-off ratio was 10 ^9.
The field effect mobility and on-off ratio of the thin film transistor were measured using a Keithley 4200-SCS (manufactured by Keithley Instruments Co., Ltd.) and a transfer curve was measured. APPLIED PHYSICS LETTERS 89, 062103 (2006) It was calculated by using the calculation method described in 1.

Examples 2-5 and Comparative Examples 1-4
A target was produced in the same manner as in Example 1 except that the composition of the target was set as shown in Table 1. Next, using the obtained target, a crystalline oxide semiconductor thin film and a thin film transistor were manufactured in the same manner as in Example 1 except that the film formation conditions and the heat treatment conditions were changed to the conditions shown in Table 1. The obtained crystalline oxide semiconductor thin film and thin film transistor were evaluated in the same manner as in Example 1. The results are shown in Table 1.
A radial distribution function of the crystalline oxide semiconductor thin film manufactured in Example 2 is shown in FIG.
The radial distribution function of the crystalline oxide semiconductor thin film produced in Examples 3, 4 and 5 is shown in FIG.
The radial distribution function of the crystalline oxide semiconductor thin film produced in Comparative Examples 1 to 4 is shown in FIG.

Example 6
Sixteen targets having a target composition in the range of Zn / (In + Zn) = 0.0001 to 0.13 (atomic ratio) were produced in the same manner as in Example 1. Next, using these targets, amorphous oxide semiconductor films were formed in the same manner as in Example 1. It was confirmed by X-ray crystal structure analysis that the obtained amorphous oxide semiconductor thin film was polycrystalline.

Using these amorphous oxide semiconductor thin films, a crystalline oxide semiconductor thin film was prepared using an electric furnace as the heat treatment apparatus, an oxygen partial pressure of 25000 Pa, a heat treatment temperature of about 300 ° C., and a heat treatment time of 1 hour.
For these crystalline oxide semiconductor thin films, the electron carrier concentration and the electron mobility were measured in the same manner as in Example 1. The results are shown in FIG.

From the obtained figure, it was confirmed that the electron mobility with respect to the electron carrier concentration increased in a logarithmic proportion in the range of the electron carrier concentration of 1 × 10 ¹⁶ to 1 × 10 ²⁰ / cm ³ . In addition, when A / B was measured similarly to Example 1 about the crystalline oxide semiconductor thin film manufactured in Example 6, all satisfy | filled the relationship of 0.1 <A / B <1.

Comparative Example 5
Twelve targets having a target composition in the range of Zn / (In + Zn) = 0.0001 to 0.13 (atomic ratio) were produced in the same manner as in Comparative Example 1. Next, using these targets, amorphous oxide semiconductor films were formed in the same manner as in Comparative Example 1, respectively. It was confirmed by X-ray crystal structure analysis that the obtained amorphous oxide semiconductor thin film was polycrystalline.

Using these amorphous oxide semiconductor thin films, a crystalline oxide semiconductor thin film was produced using an electric furnace as the heat treatment apparatus, an oxygen partial pressure of 20000 Pa, a heat treatment temperature of about 180 ° C., and a heat treatment time of 1 hour.
For these crystalline oxide semiconductor thin films, the electron carrier concentration and the electron mobility were measured in the same manner as in Example 1. The results are shown in FIG.

From the figure obtained, it was confirmed that the electron mobility with respect to the electron carrier concentration did not increase logarithmically in the range of the electron carrier concentration of 1 × 10 ¹⁶ to 1 × 10 ²⁰ / cm ³ . In addition, when A / B was measured similarly to Example 1 about the crystalline oxide semiconductor thin film manufactured by the comparative example 5, all did not satisfy | fill the relationship of 0.1 <A / B <1.

  In the crystalline oxide semiconductor of the present invention, the electron mobility increases as the electron carrier concentration increases, so that the semiconductor characteristics can be easily set. For example, the crystalline oxide semiconductor of the present invention can improve TFT characteristics such as an on-off ratio that is easy to increase and an off-current that hardly increases.

  The crystalline oxide semiconductor of the present invention can be suitably used as a transparent electrode for various display devices such as liquid crystal display devices and EL display devices.

It is a schematic sectional drawing which shows one Embodiment of the thin-film transistor of this invention. It is a figure which shows the radial distribution function of the crystalline oxide semiconductor thin film produced in Example 1 and 2. It is a figure which shows the radial distribution function of the crystalline oxide semiconductor thin film produced in Example 1, 3, 4, and 5. FIG. It is a figure which shows the radial distribution function of the crystalline oxide semiconductor thin film produced in Comparative Examples 1-4. 7 is a graph showing the relationship between the electron carrier concentration and mobility of a crystalline oxide semiconductor thin film manufactured in Example 6. FIG. 10 is a graph showing the relationship between electron carrier concentration and mobility of a crystalline oxide semiconductor thin film manufactured in Comparative Example 5. FIG.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Thin-film transistor 10 Glass substrate 20 Gate electrode 30 Gate insulating film 40 Crystalline oxide semiconductor thin film 50 Source electrode 52 Drain electrode

Claims (8)

Containing indium and zinc element (Zn) ;
In the radial distribution function (RDF) obtained by X-ray absorption spectroscopy, the maximum value of RDF with an interatomic distance between 0.3 nm and 0.36 nm is A, and the interatomic distance is between 0.1 nm and 0.2 nm. in the case where the maximum value of RDF between is B, meets 0.1 <a / B <1 relationship,
A crystalline oxide semiconductor in which an atomic ratio of indium (In) and Zn satisfies the following formula .
Zn / (Zn + In) = 0.0001 to 0.13   2. The crystalline oxide semiconductor according to claim 1, wherein a peak component is not included between a valence band peak caused by an oxygen 2p orbit and a peak caused by conduction electrons in X-ray electron spectroscopy (XPS). A polycrystalline oxide exhibiting a bixbite type crystal structure, and
The crystalline oxide semiconductor according to claim 1, wherein the electron carrier concentration is less than 1 × 10 ¹⁸ cm ⁻³ .   The crystalline oxide semiconductor according to claim 1, which has a range in which the electron mobility with respect to the electron carrier concentration increases logarithmically in proportion to the increase in the electron carrier concentration. The crystalline oxide semiconductor according to any one of claims 1 to 4 , wherein the content of a positive trivalent or higher metal element having an ionic radius of 0.7 to 0.92? Is 4000 ppm or less. Using a target containing indium and zinc element (Zn) and having an atomic ratio [Zn / (Zn + In)] of indium (In) and Zn of 0.0001 to 0.13, the water pressure in the system is 10 ^−3. A step of forming an amorphous oxide semiconductor film by sputtering on a substrate of 100 ° C. or lower as Pa or lower ,
A step of producing a crystalline oxide semiconductor by heat-treating the amorphous oxide semiconductor at an oxygen partial pressure of 21000 Pa or more in the system and a heating temperature of 250 ° C. or more for 0.1 to 120 minutes. The manufacturing method of the crystalline oxide semiconductor in any one of 1-5 . A thin film transistor using a crystalline oxide semiconductor according to the active layer to one of claims 1 to 5. The thin film transistor according to claim 7 , wherein an amorphous oxide semiconductor is used for a source electrode, a drain electrode, and a gate electrode.

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