WO2011148614A1 - 酸化物焼結体、それからなるターゲット及び酸化物半導体薄膜 - Google Patents
酸化物焼結体、それからなるターゲット及び酸化物半導体薄膜 Download PDFInfo
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- WO2011148614A1 WO2011148614A1 PCT/JP2011/002873 JP2011002873W WO2011148614A1 WO 2011148614 A1 WO2011148614 A1 WO 2011148614A1 JP 2011002873 W JP2011002873 W JP 2011002873W WO 2011148614 A1 WO2011148614 A1 WO 2011148614A1
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- thin film
- oxide
- sintered body
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- H01L29/786—Thin film transistors, i.e. transistors with a channel being at least partly a thin film
- H01L29/7869—Thin film transistors, i.e. transistors with a channel being at least partly a thin film having a semiconductor body comprising an oxide semiconductor material, e.g. zinc oxide, copper aluminium oxide, cadmium stannate
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- Y10S977/89—Deposition of materials, e.g. coating, cvd, or ald
Definitions
- the present invention relates to an oxide sintered body, a target comprising the same, and an oxide semiconductor thin film.
- TFTs thin film transistors
- LCD liquid crystal display devices
- EL electroluminescence display devices
- FED field emission displays
- a silicon semiconductor compound As a material for a semiconductor layer (channel layer) which is a main member of a field effect transistor, a silicon semiconductor compound is most widely used.
- a silicon single crystal is used for a high-frequency amplifying element or an integrated circuit element that requires high-speed operation.
- an amorphous silicon semiconductor (amorphous silicon) is used for a liquid crystal driving element or the like because of a demand for a large area.
- an amorphous silicon thin film can be formed at a relatively low temperature, its switching speed is slower than that of a crystalline thin film, so when used as a switching element for driving a display device, it may not be able to follow the display of high-speed movies. is there.
- amorphous silicon having a mobility of 0.5 to 1 cm 2 / Vs could be used, but when the resolution is SXGA, UXGA, QXGA or higher, 2 cm 2 / Mobility greater than Vs is required.
- the driving frequency is increased in order to improve the image quality, higher mobility is required.
- the crystalline silicon-based thin film has a high mobility
- problems such as requiring a large amount of energy and the number of processes for manufacturing, and a problem that it is difficult to increase the area.
- laser annealing using a high temperature of 800 ° C. or higher and expensive equipment is necessary.
- a crystalline silicon-based thin film is difficult to reduce costs such as a reduction in the number of masks because the element configuration of a TFT is usually limited to a top gate configuration.
- an oxide semiconductor thin film is produced by sputtering using a target (sputtering target) made of an oxide sintered body.
- a target sputtering target
- an oxide semiconductor thin film in which aluminum is doped in indium oxide is disclosed (Patent Document 1).
- an oxide semiconductor element is manufactured using a target having an atomic ratio Al / (Al + In) of indium to aluminum of 0.005.
- the evaluation on the performance of the target and the examination on the nodules generated during sputtering have not been sufficient.
- An object of the present invention is to provide an oxide sintered body that suppresses abnormal discharge that occurs when an oxide semiconductor thin film is formed using a sputtering method, and that allows the oxide semiconductor thin film to be obtained stably and with good reproducibility. It is to be.
- the inventors of the present invention use a sputtering target having an atomic ratio of Al / (In + Al) of 0.01 to 0.08 in an oxide sintered body composed of an aluminum element, an indium element, and an oxygen element.
- An oxide semiconductor thin film was formed.
- the inventors have found that the following relationship exists between the crystal structure of the target and the occurrence of abnormal discharge during film formation. That is, in the case where the indium oxide crystal of the target is substantially composed only of the bixbite structure, abnormal discharge does not occur even when direct current is applied, but the crystal is added to the bixbite structure in addition to Al 2 O 3 or the like. It was discovered that abnormal discharges occur frequently when other structures are included. Furthermore, even when the oxide sintered body has a bixbite structure, if the atomic ratio Al / (In + Al) is less than 0.01, abnormal discharge is likely to occur and nodules are formed. The headline and the present invention were completed.
- the following oxide sintered bodies and the like are provided.
- An indium oxide powder having an average particle size of less than 1.2 ⁇ m and an aluminum oxide powder having an average particle size of less than 1.2 ⁇ m are mixed so that the atomic ratio Al / (Al + In) is 0.01 to 0.08.
- Preparing a mixed powder 2.
- a display device comprising the thin film transistor according to 8.7.
- the oxide sintered compact which can suppress the abnormal discharge which generate
- FIG. 3 is a diagram showing the results of X-ray diffraction measurement of a sintered body produced in Example 1.
- FIG. 6 is a diagram showing a result of X-ray diffraction measurement of a sintered body produced in Example 2.
- FIG. 6 is a diagram showing the results of X-ray diffraction measurement of a sintered body produced in Example 3.
- the oxide sintered body of the present invention contains oxides of indium and aluminum, and the atomic ratio Al / (Al + In) is 0.01 to 0.08.
- Al / (Al + In) is in the above range, aluminum is in a solid solution state in indium oxide having a bixbite structure, and a low-resistance oxide sintered body is obtained.
- the oxide sintered body of the present invention has low resistance because aluminum atoms are dissolved in indium oxide having a bixbite structure, and can suppress the occurrence of abnormal discharge. Moreover, since the oxide sintered body of the present invention contains indium oxide having a bixbite structure in which aluminum atoms are dissolved, it is possible to reduce the generation of cracks and nodules in the target made of the oxide sintered body of the present invention. . Therefore, the oxide sintered body of the present invention can form a high-quality oxide semiconductor thin film efficiently, inexpensively and with energy saving.
- the bixbite structure can be confirmed by XRD measurement.
- the oxide sintered body of the present invention comprises indium oxide having a bixbite structure.
- XRD measurement X-ray diffraction measurement
- the oxide sintered body of the present invention is preferably made of indium oxide substantially having a bixbite structure, in which aluminum atoms are solid-solved, and the atomic ratio Al / (Al + In) is 0.01 to 0. .08. “Substantially” means that the effect of the present invention is attributable to the above bixbite structure, or 90% by volume or more, preferably 95% by volume or more, more preferably 98% by volume or more of the crystal structure of the oxide sintered body. Means an indium oxide crystal having a bixbite structure.
- the oxide sintered body of the present invention preferably has a crystal structure of 90% by volume or more, more preferably 95% by volume or more, and still more preferably 98% by volume or more.
- 90% by volume or more is composed of a crystal structure
- 90% by volume of the crystal structure is indium oxide showing a bixbite structure.
- Volume fraction can be calculated from X-ray diffraction peak analysis.
- Al By setting the atomic ratio Al / (Al + In) to 0.08 or less, Al can be uniformly dispersed in the indium oxide crystal. On the other hand, when the atomic ratio Al / (Al + In) exceeds 0.08, Al is not uniformly dispersed in the bixbite structure of indium oxide, and Al 2 O 3 or the like may be precipitated. If the oxide sintered body includes another crystal structure such as Al 2 O 3 , abnormal sputtering may easily occur when a target made of the oxide crystal is sputtered. The reason for the abnormal discharge is that the impedance of the discharge system including the target fluctuates during sputtering because the target is non-uniform and there is a portion where the specific resistance is locally different. The portion where the specific resistance is locally different is a crystal such as Al 2 O 3 , and reducing the crystal size and number density is effective in suppressing abnormal discharge.
- the resistance of the oxide sintered body may increase. If the target resistance increases, abnormal discharge may occur.
- the atomic ratio Al / (Al + In) of the aluminum metal and the indium metal in the oxide sintered body of the present invention is preferably 0.01 to 0.08, more preferably 0.01 to 0. .05, and more preferably 0.01 to 0.03.
- the atomic ratio of each element contained in the oxide sintered body of the present invention can be determined by analyzing the contained elements using an inductively coupled plasma emission spectrometer (ICP-AES).
- ICP-AES inductively coupled plasma emission spectrometer
- a solution sample is atomized with a nebulizer and introduced into an argon plasma (about 6000 to 8000 ° C.)
- the elements in the sample are excited by absorbing thermal energy, and orbital electrons are generated. Move from the ground state to a high energy level orbit. These orbital electrons move to a lower energy level orbit in about 10 ⁇ 7 to 10 ⁇ 8 seconds. At this time, the energy difference is emitted as light to emit light.
- the presence of the element can be confirmed by the presence or absence of the spectral line (qualitative analysis).
- the magnitude (luminescence intensity) of each spectral line is proportional to the number of elements in the sample, the sample concentration can be obtained by comparing with a standard solution having a known concentration (quantitative analysis).
- the atomic ratio of each element can be calculated
- the density of the oxide sintered body of the present invention is preferably 6.0 g / cm 3 or more, more preferably 6.3 g / cm 3 or more, and further preferably 6.4 g / cm 3 or more.
- the density of the oxide sintered body is particularly preferably 6.3 g / cm 3 or more and 7.1 g / cm 3 or less.
- the maximum particle size of the indium oxide crystal in which aluminum atoms in the oxide sintered body are dissolved is preferably 5 ⁇ m or less.
- the grain size of the indium oxide crystal exceeds 5 ⁇ m, it may cause nodules.
- the cutting speed varies depending on the direction of the crystal plane, and irregularities are generated on the target surface.
- the size of the unevenness depends on the crystal grain size present in the sintered body, and in the target made of a sintered body having a large crystal grain size, the unevenness becomes large and nodules are generated from the convex part. It is done.
- the maximum particle size of the indium oxide crystal is such that when the shape of the sputtering target made of the oxide sintered body of the present invention is a circle, the center point (one place) of the circle and two centers orthogonal to each other at the center point At a total of five intermediate points (four locations) between the center point on the line and the peripheral edge, or when the sputtering target has a quadrilateral shape, the center point (one location) and the center point on the diagonal of the quadrangle Measure the maximum diameter of the largest particles observed in a 100 ⁇ m square frame at a total of five points at the midpoint (4 points) with the corner, and determine the maximum particle size in each of these five frames. Average value of particle diameter. As for the particle diameter, the major axis of the crystal grain is measured. The crystal grains can be observed with a scanning electron microscope (SEM).
- the diameter of the aggregate of dispersed aluminum atoms is preferably less than 1 ⁇ m.
- Stable sputter discharge can be achieved by finely dispersing aluminum atoms.
- the diameter of the aggregate of aluminum atoms can be measured by EPMA (electron beam microanalyzer).
- the film formation rate during DC sputtering depends on the specific resistance of the oxide sintered body of the sputtering target. Therefore, from the viewpoint of productivity, the specific resistance of the oxide sintered body is preferably as low as possible, and the specific resistance of the oxide sintered body of the present invention is preferably 0.1 ⁇ cm or less, more preferably 0.00. 01 ⁇ cm or less. By setting the specific resistance to 0.01 ⁇ cm or less, a faster film formation rate can be realized. On the other hand, when the specific resistance of the oxide sintered body is more than 0.1 ⁇ cm, it may be difficult to perform stable film formation by direct current sputtering. In addition, the specific resistance of the oxide sintered body can be reduced by a reduction process in which heating is performed in a non-oxidizing atmosphere such as nitrogen in the process of manufacturing the sintered body described later.
- the specific resistance of the oxide sintered body is 0.1 ⁇ cm or less, stable DC sputtering cannot always be performed. Even if the specific resistance of the entire oxide sintered body is 0.1 ⁇ cm or less, the oxide sintered body locally includes a high-resistance material phase exceeding 0.1 ⁇ cm (for example, the above-described Al 2 O 3 phase). If this is the case, the portion is charged by irradiation with sputtering gas ions, so that abnormal discharge occurs, and DC sputtering cannot be performed stably. Therefore, it is important that the specific resistance of the whole oxide sintered body is 0.1 ⁇ cm or less without locally including the high resistance phase.
- the oxide sintered body of the present invention contains an oxide composed of an aluminum element, an indium element and an oxygen element, and preferably consists essentially of indium oxide having a bixbite structure, but does not impair the effects of the present invention. In addition, inevitable impurities may be included.
- an indium oxide powder having an average particle size of less than 1.2 ⁇ m and an aluminum oxide powder having an average particle size of less than 1.2 ⁇ m have an atomic ratio of Al / (Al + In) of 0.
- the oxide sintered body of the present invention is not limited by its production method and can be produced from a combination of aluminum metal and indium oxide, but it is preferable to use indium oxide and aluminum oxide as raw material powder.
- indium oxide and aluminum oxide as the raw material powder, aluminum metal particles are present in the obtained oxide sintered body, and the metal particles are melted on the surface of the target during film formation. There is a possibility that the composition of the obtained film and the composition of the oxide sintered body are greatly different from each other without being released.
- Both the indium oxide powder and the aluminum oxide powder which are raw material powders, have an average particle size of less than 1.2 ⁇ m, preferably 1.0 ⁇ m or less.
- the average particle diameter of the indium oxide powder or the aluminum oxide powder is 1.2 ⁇ m or more, the aluminum atoms may not be uniformly dispersed in the indium oxide (In 2 O 3 ) crystal.
- the average particle size of the raw material powder can be measured with a laser diffraction particle size distribution device or the like.
- In 2 O 3 powder and Al 2 O 3 powder are mixed so that the atomic ratio Al / (Al + In) is 0.01 to 0.08.
- the atomic ratio Al / (Al + In) is 0.08 or less, an oxide sintered body substantially composed of indium oxide having a bixbite structure can be obtained.
- the raw material powder can be mixed using a wet or dry ball mill, vibration mill, bead mill, or the like.
- a bead mill mixing method is most preferable because the crushing efficiency of the agglomerates is high in a short time and the additive is well dispersed.
- the mixing time is preferably 15 hours or longer, more preferably 19 hours or longer. This is because if the mixing time is insufficient, a crystal structure different from the bixbite structure such as Al 2 O 3 may be formed in the finally obtained oxide sintered body.
- the mixing time varies depending on the size of the apparatus to be used and the amount of slurry to be processed, but it is preferable to adjust the particle size distribution in the slurry to be uniform at 1 ⁇ m or less.
- binder When mixing the raw material powder, an arbitrary amount of binder may be added and mixed at the same time.
- binder polyvinyl alcohol, vinyl acetate, or the like can be used.
- a molded body can be produced by blending a mixed raw material powder with an aqueous solvent to form a raw material powder slurry, and molding the granulated powder obtained by granulating the raw material powder slurry.
- the granulation is preferably performed by quick drying granulation.
- a spray dryer is widely used as an apparatus for rapid drying granulation. Specific drying conditions are determined by various conditions such as the slurry concentration of the slurry to be dried, the temperature of hot air used for drying, and the amount of air. In implementation, it is necessary to obtain optimum conditions in advance.
- the In 2 O 3 powder and the Al 2 O 3 powder may be separated, and a uniform granulated powder may not be obtained.
- Al 2 O 3 or the like may be generated inside the sintered body, causing abnormal discharge in sputtering.
- the granulated powder can be molded by a mold press or a cold isostatic press (CIP), and the pressure at the time of molding is, for example, 1.2 ton / cm 2 or more.
- CIP cold isostatic press
- a pressure sintering method such as hot press, oxygen pressurization, hot isostatic pressurization and the like can be employed in addition to the atmospheric pressure sintering method.
- a normal pressure sintering method from the viewpoints of reducing manufacturing cost, possibility of mass production, and easy production of a large sintered body.
- the compact is sintered in an air atmosphere or an oxidizing gas atmosphere, and preferably sintered in an oxidizing gas atmosphere.
- the oxidizing gas atmosphere is preferably an oxygen gas atmosphere.
- the oxygen gas atmosphere is preferably an atmosphere having an oxygen concentration of, for example, 10 to 100 vol%.
- the density of the oxide sintered body can be further increased by introducing an oxygen gas atmosphere in the temperature raising process.
- the firing temperature is 1100 ° C. to 1550 ° C.
- the firing time is 8 hours or longer.
- Al does not dissolve in the indium oxide crystal, and an Al 2 O 3 phase or the like is deposited inside the target, causing abnormal discharge. There is a risk.
- the firing temperature exceeds 1550 ° C., the average crystal grain size increases and coarse pores are generated due to remarkable crystal grain growth, which may cause a decrease in sintered body strength and abnormal discharge.
- the firing temperature is preferably 1200 to 1550 ° C., more preferably 1250 to 1500 ° C., and particularly preferably 1300 to 1450 ° C.
- the firing time is preferably 10 to 50 hours, more preferably 11 to 40 hours, and particularly preferably 12 to 30 hours.
- the heating rate during firing is preferably 1 to 15 ° C./min in the temperature range of 500 to 1500 ° C.
- the temperature range of 500-1500 ° C. is the range where sintering proceeds most. If the rate of temperature rise in this temperature range is less than 1 ° C./min, crystal grain growth becomes significant, and there is a possibility that densification cannot be achieved. On the other hand, if the rate of temperature rise exceeds 15 ° C./min, the thermal uniformity in the sintering furnace is lowered, so that the amount of shrinkage during sintering is distributed and the sintered body may be cracked.
- the obtained sintered body may be further provided with a reduction step as necessary.
- the reduction step is for making the bulk resistance of the sintered body obtained in the firing step uniform over the entire sintered body.
- Examples of the reduction method that can be applied in the reduction step include firing in a reducing gas, vacuum firing, reduction treatment by firing in an inert gas, and the like.
- reduction treatment by firing in a reducing gas hydrogen, methane, carbon monoxide, a mixed gas of these gases and oxygen, or the like can be used.
- reduction treatment by firing in an inert gas nitrogen, argon, a mixed gas of these gases and oxygen, or the like can be used.
- the temperature during the reduction treatment is usually 100 to 800 ° C., preferably 200 to 800 ° C.
- the reduction treatment time is usually 0.01 to 10 hours, preferably 0.05 to 5 hours.
- An example of the method for producing the oxide sintered body of the present invention is as follows. An aqueous solvent is blended with the raw material powder containing a mixed powder of indium oxide powder and aluminum oxide powder, and the resulting slurry is mixed for 12 hours or more, and then solid-liquid separation, drying and granulation are performed. The granulated product is molded in a mold, and the resulting molded product is fired at 1100 ° C. to 1550 ° C. for 8 hours or more in an oxygen atmosphere to obtain an oxide sintered body.
- the sintered body density is 6.0 g / cm 3 or more, the specific resistance is 0.1 ⁇ cm or less, and the average crystal grain size is 10 ⁇ m. It is possible to obtain an oxide sintered body having only a bixbite structure of indium oxide in which aluminum atoms are substantially dissolved as follows.
- a sputtering target can be obtained by processing the oxide sintered body of the present invention.
- a sputtering target can be obtained by cutting the oxide sintered body of the present invention into a shape suitable for mounting on a sputtering apparatus.
- the thickness of the target material after cutting is usually 2 to 20 mm, preferably 3 to 12 mm, particularly preferably 4 to 6 mm.
- the sintered body is ground by, for example, a surface grinder to obtain a material having a surface roughness Ra of 5 ⁇ m or less.
- the sputter surface of the target material may be further mirror-finished so that the average surface roughness Ra may be 1000 angstroms or less.
- a known polishing technique such as mechanical polishing, chemical polishing, and mechanochemical polishing (a combination of mechanical polishing and chemical polishing) can be used.
- polishing to # 2000 or more with a fixed abrasive polisher polishing liquid: water
- lapping with loose abrasive lapping abrasive: SiC paste, etc.
- lapping by changing the abrasive to diamond paste can be obtained by:
- Such a polishing method is not particularly limited.
- the surface of the target material is preferably finished with a diamond grindstone of No. 200 to 10,000, and particularly preferably finished with a diamond grindstone of No. 400 to 5,000. If a diamond grindstone smaller than 200 or larger than 10,000 is used, the target material may be easily broken.
- the target material has a surface roughness Ra of 0.5 ⁇ m or less and has a non-directional ground surface. If Ra is larger than 0.5 ⁇ m or the polished surface has directivity, abnormal discharge may occur or particles may be generated.
- the target material after cutting may be cleaned.
- air blow or running water washing can be used.
- air blow When removing foreign matter by air blow, it is possible to remove the foreign matter more effectively by suctioning with a dust collector from the opposite side of the nozzle.
- ultrasonic cleaning or the like can be further performed. This ultrasonic cleaning is effective by performing multiple oscillations at a frequency of 25 to 300 KHz. For example, it is preferable to perform ultrasonic cleaning by multiplying twelve types of frequencies in 25 KHz increments between frequencies of 25 to 300 KHz.
- the sputtering target made of the oxide sintered body of the present invention can be obtained by bonding the target material obtained as described above to the backing plate. Further, a plurality of target materials may be attached to one backing plate to substantially serve as one target.
- the oxide semiconductor thin film of the present invention can be obtained by forming a film using the target made of the oxide sintered body of the present invention.
- the film formation can be performed by, for example, a vapor deposition method, a sputtering method, an ion plating method, a pulse laser vapor deposition method, or the like.
- the oxide semiconductor thin film obtained by forming a film by a sputtering method or the like using a target composed of the oxide sintered body of the present invention has a small lattice constant because aluminum is dissolved in the indium oxide crystal. The overlap of 5s orbitals between indium in the crystal becomes large, and an improvement in mobility can be expected.
- Al dissolved in the In site reduces oxygen vacancies, a decrease in carrier concentration can be expected.
- the oxide sintered body of the present invention has high conductivity, a DC sputtering method having a high film formation rate can be applied.
- the oxide sintered body of the present invention can also be applied with an RF sputtering method, an AC sputtering method, and a pulsed DC sputtering method, and any method does not cause abnormal discharge. Sputtering is possible.
- the sputtering gas a mixed gas of argon and an oxidizing gas can be used.
- the oxidizing gas include O 2 , CO 2 , O 3 , and H 2 O.
- the oxygen partial pressure during sputtering film formation is preferably 5% or more and 40% or less.
- a thin film formed under a condition where the oxygen partial pressure is less than 5% has conductivity and may be difficult to use as an oxide semiconductor.
- the oxygen partial pressure is 10% or more and 40% or less.
- the substrate temperature during film formation is, for example, 500 ° C. or lower, preferably 10 ° C. or higher and 400 ° C. or lower, more preferably 20 ° C. or higher and 350 ° C. or lower, and particularly preferably 80 ° C. or higher and 300 ° C. or lower.
- the water pressure during sputtering film formation is preferably 5 ⁇ 10 ⁇ 4 to 7 ⁇ 10 ⁇ 2 Pa.
- the water pressure is less than 5 ⁇ 10 ⁇ 4 Pa, microcrystals may be formed in the film immediately after the thin film is deposited.
- the water pressure is more than 7 ⁇ 10 ⁇ 2 Pa, the film density is significantly reduced, so that the overlap of In5s orbitals is reduced and the mobility may be reduced.
- the thin film By annealing the thin film on the substrate formed by sputtering, the thin film is crystallized to obtain semiconductor characteristics.
- Al is solid-solved in the indium oxide crystal by annealing, and exhibits a single phase of bixbite.
- the annealing temperature is, for example, 500 ° C. or less, preferably 100 ° C. or more and 500 ° C. or less, more preferably 150 ° C. or more and 400 ° C. or less, and particularly preferably 200 ° C. or more and 350 ° C. or less.
- the heating atmosphere during film formation and annealing is not particularly limited, but an air atmosphere or an oxygen circulating atmosphere is preferable from the viewpoint of carrier controllability.
- a lamp annealing device, a laser annealing device, a thermal plasma device, a hot air heating device, a contact heating device, or the like can be used in the presence or absence of oxygen.
- the oxide semiconductor thin film of the present invention thus obtained contains oxides of indium and aluminum, and the atomic ratio Al / (Al + In) in the thin film is 0.01 to 0.08. It consists essentially of indium oxide having a bite structure, in which aluminum is dissolved in indium oxide, and the atomic ratio Al / (Al + In) in the thin film is 0.01 to 0.08.
- the atomic ratio Al / (Al + In) of the thin film shows the same value as the atomic ratio Al / (Al + In) of the target (sintered body) used for forming the thin film.
- the oxide semiconductor thin film of the present invention can be used for a thin film transistor, and is particularly suitable for a channel layer of a thin film transistor.
- a thin film transistor including the oxide semiconductor thin film of the present invention as a channel layer (hereinafter sometimes referred to as a thin film transistor of the present invention). ) May be a channel etch type. Since the oxide semiconductor thin film of the present invention is a crystalline film and has durability, in the manufacture of the thin film transistor of the present invention, a photolithography process for forming a source / drain electrode and a channel part by etching a metal thin film such as Mo is also performed. It becomes possible.
- the thin film transistor of the present invention may be an etch stopper.
- the etch stopper can protect the channel portion formed of the semiconductor layer, and a large amount of oxygen is taken into the semiconductor layer during film formation through the etch stopper layer. There is no need to supply oxygen from the outside.
- Example 1-3 An indium oxide powder having an average particle size of 0.98 ⁇ m and an aluminum oxide powder having an average particle size of 0.97 ⁇ m are weighed so as to have the atomic ratio Al / (Al + In) shown in Table 1, and then uniformly pulverized and mixed for molding. A binder was added and granulated. Next, this raw material mixed powder was uniformly filled into a mold, and pressure-molded with a cold press machine at a press pressure of 140 MPa. The molded body thus obtained was fired in a sintering furnace at the firing temperature and firing time shown in Table 1 to produce a sintered body. The firing atmosphere was an oxygen atmosphere during the temperature increase, and the other was in the air (atmosphere).
- the firing was performed at a temperature increase rate of 1 ° C./min and a temperature decrease rate of 15 ° C./min.
- the average particle size of the raw material oxide powder used was measured with a laser diffraction particle size distribution analyzer SALD-300V (manufactured by Shimadzu Corporation), and the median particle size D50 was used.
- the crystal structure of the obtained sintered body was examined with an X-ray diffraction measurement device (Rigaku Ultimate-III).
- An X-ray chart of the sintered body of Example 1-3 is shown in FIG.
- the crystal structure can be confirmed with a JCPDS (Joint Committee of Powder Diffraction Standards) card.
- the bixbite structure of indium oxide is JCPDS card no. 06-0416.
- XRD X-ray diffraction measurement
- the density of the obtained sintered body was calculated from the weight and outer dimensions of the sintered body cut into a certain size. Further, the bulk resistance (conductivity) of the obtained sintered body was measured based on a four-probe method (JIS R 1637) using a resistivity meter (Made by Mitsubishi Chemical Corporation, Loresta). The results are shown in Table 1.
- the dispersion of Al was examined by EPMA measurement for the obtained sintered body. As a result, an aggregate of aluminum atoms of 1 ⁇ m or more was not observed, and it was found that the sintered body of Example 1-3 was extremely excellent in dispersibility and uniformity.
- Example 1-3 The surface of the oxide sintered body obtained in Example 1-3 was ground with a surface grinder, the sides were cut with a diamond cutter, and bonded to a backing plate to obtain a sputtering target having a diameter of 4 inches each.
- the obtained sputtering target is mounted on a DC sputtering apparatus, and argon is used as a sputtering gas, sputtering pressure is 0.4 Pa, substrate temperature is room temperature, DC output is 400 W, 10 kWh is continuously sputtered, and voltage fluctuation during sputtering.
- argon is used as a sputtering gas
- sputtering pressure is 0.4 Pa
- substrate temperature is room temperature
- DC output 400 W
- 10 kWh is continuously sputtered
- voltage fluctuation during sputtering was stored in a data logger and the presence or absence of abnormal discharge was confirmed.
- Table 1 The presence or absence of the abnormal discharge was performed by monitoring the voltage fluctuation and detecting the abnormal discharge. Specifically, the abnormal discharge was determined when the voltage fluctuation generated during the measurement time of 5 minutes was 10% or more of the steady voltage during the sputtering operation.
- the atmosphere was a mixed gas obtained by adding 3% hydrogen gas to argon gas, and sputtering was performed continuously for 30 hours to check for the occurrence of nodules. did.
- the sputtering conditions are a sputtering pressure of 0.4 Pa, a DC output of 100 W, a substrate temperature: room temperature, and the hydrogen gas added to the atmosphere gas promotes the generation of nodules.
- nodules For the nodules, a change in the target surface after sputtering was observed 50 times with a stereomicroscope, and a method of measuring the number average of nodules of 20 ⁇ m or more generated in a visual field of 3 mm 2 was adopted. Table 1 shows the number of nodules generated.
- Comparative Example 1-3 An indium oxide powder having an average particle size of 0.98 ⁇ m and an aluminum oxide powder having an average particle size of 0.97 ⁇ m are weighed so as to have an atomic ratio of Al / (Al + In) shown in Table 2, and at the firing temperature and firing time shown in Table 2. A sintered body and a target were produced and evaluated in the same manner as in Example 1-3 except that firing was performed. The results are shown in Table 2. In Comparative Example 1, a sintered body and a target were manufactured using only indium oxide powder.
- Comparative Examples 4 and 5 Instead of aluminum oxide, yttrium oxide powder (Y 2 O 3 powder) having an average particle diameter of 1.06 ⁇ m was used in Comparative Example 4, and boron oxide powder (B 2 O 3 powder) having an average particle diameter of 1.02 ⁇ m was used in Comparative Example 5.
- Y 2 O 3 powder yttrium oxide powder
- B 2 O 3 powder boron oxide powder
- Table 2 were respectively weighed so that the atomic ratio M (M + In) shown in Table 2 was obtained and fired at the firing temperature and firing time shown in Table 2 to produce sintered bodies and targets in the same manner as in Example 1-3. ,evaluated. The results are shown in Table 2.
- the crystal structure was examined with an X-ray diffraction measurement apparatus in the same manner as in Example 1-3.
- an Al 2 O 3 phase having a corundum structure was observed in addition to the bixbite structure in the X-ray diffraction chart.
- the crystal structure can be confirmed with a JCPDS card.
- argon 9.9 sccm and water 0.1 sccm water pressure: 4.0 ⁇ 10 ⁇ 3 Pa
- water pressure 4.0 ⁇ 10 ⁇ 3 Pa
- the crystal structure immediately after film formation of the thin film formed on the glass substrate was confirmed by XRD. As a result, a clear diffraction peak was not observed, and it was confirmed to be amorphous.
- the glass substrate on which this thin film was formed was put into a heating furnace heated to 300 ° C. in air and treated for 1 hour. When the XRD measurement was performed on the annealed thin film, only the peak of the bixbite structure of indium oxide was observed.
- the crystal structure is JCPDS card no. Can be confirmed at 06-0416.
- the carrier concentration and mobility of the thin film after annealing were evaluated by Hall effect measurement. The carrier concentration was 6.98 ⁇ 10 17 cm ⁇ 3 and the hole mobility was 24.5 cm 2 / Vs. . It was also confirmed that the atomic ratio of the thin film after annealing was the same as the atomic ratio of the target used.
- a metal mask was placed on a silicon substrate (conductive silicon substrate) on which a thin film was formed, a channel portion of L: 200 ⁇ m and W: 1000 ⁇ m was formed, and gold was deposited to form source / drain electrodes.
- the element was placed in a heating furnace heated to 300 ° C., and a thin film transistor was manufactured by performing treatment for 1 hour.
- the manufactured thin film transistor was evaluated for field effect mobility, on-off ratio, and S value. As a result, it was confirmed that the field-effect mobility was 38.8 cm 2 / Vs, the on-off ratio was 8.18 ⁇ 10 8 , normally-off characteristics, and the S value was 0.66. .
- argon 9.9 sccm and water 0.1 sccm water pressure: 4.0 ⁇ 10 ⁇ 3 Pa
- water pressure 4.0 ⁇ 10 ⁇ 3 Pa
- the crystal structure immediately after film formation of the thin film formed on the glass substrate was confirmed by XRD. As a result, a clear diffraction peak was not observed, and it was confirmed to be amorphous.
- the glass substrate on which this thin film was formed was put into a heating furnace heated to 300 ° C. in air and treated for 1 hour. When the XRD measurement was performed on the annealed thin film, only the peak of the bixbite structure of indium oxide was observed.
- the crystal structure is JCPDS card no. Can be confirmed at 06-0416.
- the carrier concentration and mobility of the thin film after annealing were evaluated by Hall effect measurement. The carrier concentration was 2.37 ⁇ 10 17 cm ⁇ 3 and the hole mobility was 22.1 cm 2 / Vs. .
- a metal mask was placed on a silicon substrate (conductive silicon substrate) on which a thin film was formed, a channel portion of L: 200 ⁇ m and W: 1000 ⁇ m was formed, and gold was deposited to form source / drain electrodes.
- the element was placed in a heating furnace heated to 300 ° C., and a thin film transistor was manufactured by performing treatment for 1 hour.
- the manufactured thin film transistor was evaluated for field effect mobility, on-off ratio, and S value. As a result, it was confirmed that the field effect mobility was 31.1 cm 2 / Vs, the on-off ratio was 3.11 ⁇ 10 8 , a normally-off characteristic was exhibited, and the S value was 0.52. .
- argon 9.9 sccm and water 0.1 sccm water pressure: 4.0 ⁇ 10 ⁇ 3 Pa
- water pressure 4.0 ⁇ 10 ⁇ 3 Pa
- the crystal structure immediately after film formation of the thin film formed on the glass substrate was confirmed by XRD. As a result, a clear diffraction peak was not observed, and it was confirmed to be amorphous.
- the glass substrate on which this thin film was formed was put into a heating furnace heated to 300 ° C. in air and treated for 1 hour. When the XRD measurement was performed on the annealed thin film, only the peak of the bixbite structure of indium oxide was observed.
- the crystal structure is JCPDS card no. Can be confirmed at 06-0416.
- the carrier concentration and mobility of the thin film after annealing were evaluated by Hall effect measurement. The carrier concentration was 5.88 ⁇ 10 16 cm ⁇ 3 and the hole mobility was 18.8 cm 2 / Vs. .
- a metal mask was placed on a silicon substrate (conductive silicon substrate) on which a thin film was formed, a channel portion of L: 200 ⁇ m and W: 1000 ⁇ m was formed, and gold was deposited to form source / drain electrodes.
- the element was placed in a heating furnace heated to 300 ° C., and a thin film transistor was manufactured by performing treatment for 1 hour.
- the manufactured thin film transistor was evaluated for field effect mobility, on-off ratio, and S value. As a result, it was confirmed that the field effect mobility was 24.3 cm 2 / Vs, the on-off ratio was 2.56 ⁇ 10 8 , a normally-off characteristic was exhibited, and the S value was 0.77. .
- argon 9.9 sccm and water 0.1 sccm water pressure: 4.0 ⁇ 10 ⁇ 3 Pa
- water pressure 4.0 ⁇ 10 ⁇ 3 Pa
- the crystal structure immediately after film formation of the thin film formed on the glass substrate was confirmed by XRD. As a result, a clear diffraction peak was not observed, and it was confirmed to be amorphous.
- the glass substrate on which this thin film was formed was put into a heating furnace heated to 300 ° C. in air and treated for 1 hour.
- the XRD measurement was performed on the annealed thin film, no clear diffraction peak was observed, and it was confirmed that the film was amorphous.
- the carrier concentration and mobility of the annealed thin film were evaluated by Hall effect measurement, the carrier concentration was 7.28 ⁇ 10 16 cm ⁇ 3 and the hole mobility was 9.7 cm 2 / Vs. It can be seen that the hole mobility is significantly inferior to the thin films of Examples 4-6.
- a metal mask was placed on a silicon substrate (conductive silicon substrate) on which a thin film was formed, a channel portion of L: 200 ⁇ m and W: 1000 ⁇ m was formed, and gold was deposited to form source / drain electrodes.
- the element was placed in a heating furnace heated to 300 ° C., and a thin film transistor was manufactured by performing treatment for 1 hour.
- the manufactured thin film transistor was evaluated for field effect mobility, on-off ratio, and S value. As a result, it was confirmed that the field effect mobility was 7.8 cm 2 / Vs, the on-off ratio was 2.43 ⁇ 10 6 , a normally-off characteristic was exhibited, and the S value was 1.87. . It can be seen that the field-effect mobility is inferior as compared with the transistors of Examples 4 to 6.
- the sputtering target made of the oxide sintered body of the present invention can be used for manufacturing thin film transistors and the like.
- the thin film transistor of the present invention can be used for an integrated circuit or the like.
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Abstract
Description
1.インジウム及びアルミニウムの酸化物を含有し、
原子比Al/(Al+In)が0.01~0.08である酸化物焼結体。
2. 平均粒径が1.2μm未満の酸化インジウム粉末、及び平均粒径が1.2μm未満の酸化アルミニウム粉末を、原子比Al/(Al+In)が0.01~0.08となるように混合して混合粉末を調製する工程、
前記混合粉末を成形して成形体を製造する工程、及び
前記成形体を1100℃~1550℃で8時間以上焼成する工程を含む1に記載の酸化物焼結体の製造方法。
3.前記焼成を酸化ガス雰囲気中で行なう2に記載の酸化物焼結体の製造方法。
4.1に記載の酸化物焼結体を加工して得られるターゲット。
5.4に記載のターゲットをスパッタリングして薄膜を成膜し、前記薄膜をアニールすることで得られる酸化物半導体薄膜であって、
原子比Al/(Al+In)が0.01~0.08であり、酸化インジウムのビックスバイト構造を有する酸化物半導体薄膜。
6.前記スパッタリングを水分圧5×10-4~7×10-2Paで行なう5に記載の酸化物半導体薄膜。
7.5又は6に記載の酸化物半導体薄膜をチャネル層として有する薄膜トランジスタ。
8.7に記載の薄膜トランジスタを備えてなる表示装置。
原子比Al/(Al+In)が上記範囲にあることにより、アルミニウムがビックスバイト構造の酸化インジウムに固溶した状態となり、低抵抗の酸化物焼結体となる。
また、本発明の酸化物焼結体は、アルミニウム原子が固溶したビックスバイト構造の酸化インジウムを含むので、本発明の酸化物燒結体からなるターゲットのクラック及びノジュールの発生を低減することができる。従って、本発明の酸化物焼結体は、高品質の酸化物半導体薄膜を、効率的に、安価に、且つ省エネルギーで成膜することができる。
上記ビックスバイト構造は、XRD測定により確認することができる。
尚、原子が規則的に並んだ結晶にX線が入射すると、特定の方向で強いX線が観察され、回折現象を生じる。これは、それぞれの位置で散乱されるX線の光路差が、X線の波長の整数倍になっていると、波の位相が一致するため、波の振幅が大きくなることで説明される。
物質はそれぞれに特有な規則性を持つ結晶をつくることから、X線回折では化合物の種類を調べることができる。また、結晶の大きさ(結晶の秩序性)、材料中に存在する結晶の方位の分布状態(結晶配向)、結晶に掛かる残留応力の評価を行うこともできる。
「実質的」とは、本発明の効果が上記ビックスバイト構造に起因すること、又は酸化物焼結体の結晶構造の90体積%以上、好ましくは95体積%以上、さらに好ましくは98体積%以上がビックスバイト構造を示す酸化インジウム結晶であることを意味する。
また、本発明の酸化物焼結体は、好ましくは90体積%以上、より好ましくは95体積%以上、さらに好ましくは98体積%以上が結晶構造で構成される。好ましくは、本発明の酸化物焼結体は、90体積%以上が結晶構造で構成され、当該結晶構造の90体積%がビックスバイト構造を示す酸化インジウムである。
X線回折ピーク解析から体積分率を算出することができる。
上記異常放電の理由としては、ターゲットが不均一で局所的に比抵抗の異なる部分が存在することで、ターゲットを含む放電系のインピーダンスがスパッタリング中に変動してしまうためである。この局所的に比抵抗が異なる部分とは、Al2O3等の結晶であり、これら結晶サイズ及び数密度を小さくすることが異常放電の抑制には効果的である。
例えばICP-AESを用いた分析の場合、溶液試料をネブライザーで霧状にし、アルゴンプラズマ(約6000~8000℃)に導入すると、試料中の元素は熱エネルギーを吸収して励起され、軌道電子が基底状態から高いエネルギー準位の軌道に移る。この軌道電子は10-7~10-8秒程度で、より低いエネルギー準位の軌道に移る。この際にエネルギーの差を光として放射し発光する。この光は元素固有の波長(スペクトル線)を示すため、スペクトル線の有無により元素の存在を確認できる(定性分析)。また、それぞれのスペクトル線の大きさ(発光強度)は試料中の元素数に比例するため、既知濃度の標準液と比較することで試料濃度を求めることができる(定量分析)。
このように、定性分析で含有されている元素を特定し、定量分析で含有量を求めることで、各元素の原子比を求めることができる。
密度が6.0g/cm3未満の場合、酸化物焼結体からなるスパッタリングターゲットの表面が黒化したりし、異常放電を誘発し、スパッタ速度が低下するおそれがある。酸化物焼結体の密度は、特に好ましくは6.3g/cm3以上7.1g/cm3以下である。
スパッタによってターゲット表面が削られる場合、その削られる速度が結晶面の方向によって異なり、ターゲット表面に凹凸が発生する。この凹凸の大きさは、焼結体中に存在する結晶粒径に依存し、大きい結晶粒径を有する焼結体からなるターゲットでは、その凹凸が大きくなり、その凸部分よりノジュールが発生すると考えられる。
結晶粒は走査型電子顕微鏡(SEM)により観察することができる。
アルミニウム原子の集合体の直径はEPMA(電子線マイクロアナライザ)により測定することができる。
尚、酸化物焼結体の比抵抗は、後述する焼結体の製造過程において、窒素等の非酸化性の雰囲気下で加熱する還元処理により低減することができる。
従って、高抵抗相を局所的に含まずに、酸化物焼結体全体の比抵抗が0.1Ωcm以下であることが重要である。
尚、原料粉末として、酸化インジウムとアルミニウム金属を用いる場合、得られる酸化物焼結体中にアルミニウムの金属粒が存在して、成膜時にターゲット表面に金属粒が溶融していることでターゲットから放出されず、得られる膜の組成と酸化物焼結体の組成とが大きく異なるおそれがある。
酸化インジウム粉末又は酸化アルミニウム粉末の平均粒径が1.2μm以上の場合、アルミニウム原子が酸化インジウム(In2O3)結晶中に均一に分散しないおそれがある。
尚、上記原料粉末の平均粒径は、レーザー回折式粒度分布装置等で測定することができる。
原子比Al/(Al+In)を0.08以下にすることにより、ビックスバイト構造を示す酸化インジウムから実質的になる酸化物焼結体を得ることができる。
混合にビーズミルを用いる場合は、混合時間は、用いる装置の大きさ及び処理するスラリー量によって異なるが、スラリー中の粒度分布がすべて1μm以下と均一になるように調整するとよい。
上記バインダーには、ポリビニルアルコール、酢酸ビニル等を用いることができる。
造粒は、急速乾燥造粒を行うことが好ましい。急速乾燥造粒するための装置としては、スプレードライヤが広く用いられている。具体的な乾燥条件は、乾燥するスラリーのスラリー濃度、乾燥に用いる熱風温度、風量等の諸条件により決定される。実施に際しては、予め最適条件を求めておくことが必要となる。
尚、自然乾燥では、原料粉末の比重差によって沈降速度が異なるため、In2O3粉末及びAl2O3粉末の分離が起こり、均一な造粒粉が得られなくなるおそれがある。この不均一な造粒粉を用いて焼結体を作製すると、焼結体内部にAl2O3等が生成する場合があり
、スパッタリングにおける異常放電の原因となる。
但し、製造コストの低減、大量生産の可能性及び容易に大型の焼結体を製造できるといった観点から、常圧焼結法を採用することが好ましい。
酸化ガス雰囲気とは、好ましくは酸素ガス雰囲気である。酸素ガス雰囲気は、酸素濃度が、例えば10~100vol%の雰囲気であるとよい。本発明の酸化物焼結体の作製においては、昇温過程にて酸素ガス雰囲気を導入することで、酸化物焼結体密度をより高くすることができる。
焼成温度が1100℃未満及び/又は焼成時間が8時間未満であると、Alが酸化インジウム結晶中に固溶せずに、Al2O3相等がターゲット内部に析出形成され、異常放電の原因となるおそれがある。一方、焼成温度が1550℃を超える場合、著しい結晶粒成長によって平均結晶粒径の増大、及び粗大空孔の発生をきたし、焼結体強度の低下や異常放電の原因となるおそれがある。
焼成時間は、好ましくは10~50時間であり、さらに好ましくは11~40時間であり、特に好ましくは12~30時間である。
500~1500℃の温度範囲は、焼結が最も進行する範囲である。この温度範囲での昇温速度が1℃/min未満では、結晶粒成長が著しくなって、高密度化を達成することができないおそれがある。一方、昇温速度が15℃/min超では、焼結炉内の均熱性が低下することで、焼結中の収縮量に分布が生じ、焼結体が割れてしまうおそれがある。
還元性ガス中での焼成による還元処理の場合、水素、メタン、一酸化炭素、又はこれらのガスと酸素との混合ガス等を用いることができる。
不活性ガス中での焼成による還元処理の場合、窒素、アルゴン、又はこれらのガスと酸素との混合ガス等を用いることができる。
上記還元処理時の温度は、通常100~800℃、好ましくは200~800℃である。また、還元処理の時間は、通常0.01~10時間、好ましくは0.05~5時間である。
酸化インジウム粉と酸化アルミニウム粉との混合粉を含む原料粉末に、水系溶媒を配合し、得られたスラリーを12時間以上混合した後、固液分離、乾燥及び造粒する。この造粒物を型枠に入れて成形し、得られた成形体を酸素雰囲気中、1100℃~1550℃で8時間以上焼成することで酸化物焼結体とする。
切削加工後のターゲット素材の厚みは通常2~20mm、好ましくは3~12mm、特に好ましくは4~6mmである。
尚、エアーブローや流水洗浄では限界があるので、さらに超音波洗浄等を行なうこともできる。この超音波洗浄は周波数25~300KHzの間で多重発振させて行なう方法が有効である。例えば周波数25~300KHzの間で、25KHz刻みに12種類の周波数を多重発振させて超音波洗浄を行なうのがよい。
上記成膜は、例えば蒸着法、スパッタリング法、イオンプレーティング法、パルスレーザー蒸着法等により実施できる。本発明の酸化物焼結体からなるターゲットを用いてスパッタリング法等により成膜して得られる酸化物半導体薄膜は、アルミニウムが酸化インジウム結晶中に固溶しているので、格子定数を小さくし、結晶中のインジウム同士の5s軌道の重なりが大きくなって、移動度の向上が期待できる。加えて、Inサイトに固溶したAlが酸素欠損を減らすので、キャリア濃度の減少が期待できる。
本発明の酸化物焼結体は、高い導電性を有することから成膜速度の速いDCスパッタリング法を適用することができる。また、本発明の酸化物焼結体は、上記DCスパッタリング法に加えて、RFスパッタリング法、ACスパッタリング法、パルスDCスパッタリング法も適用することができ、いずれの方法であっても異常放電のないスパッタリングが可能である。
スパッタリング成膜時の酸素分圧は5%以上40%以下とすることが好ましい。酸素分圧が5%未満の条件で成膜した薄膜は導電性を有し、酸化物半導体としての利用が困難な場合がある。好ましくは、酸素分圧は10%以上40%以下である。
スパッタリング成膜時の水分圧は、好ましくは5×10-4~7×10-2Paである。水分圧が5×10-4Pa未満の場合、薄膜堆積直後に膜中に微結晶が生成するおそれがある。一方、水分圧が7×10-2Pa超の場合、膜密度の低下が顕著となるため、In5s軌道の重なりが小さくなって移動度の低下を招くおそれがある。
アニール処理においては、酸素の存在下又は不存在下で、ランプアニール装置、レーザーアニール装置、熱プラズマ装置、熱風加熱装置、接触加熱装置等を用いることができる。
尚、薄膜の原子比Al/(Al+In)は、当該薄膜の成膜に用いたターゲット(焼結体)の原子比Al/(Al+In)と同様の値を示す。
本発明の酸化物半導体薄膜をチャネル層として備える薄膜トランジスタ(以下、本発明の薄膜トランジスタと言う場合がある)は、チャネルエッチ型でもよい。本発明の酸化物半導体薄膜は、結晶膜であり耐久性があるので、本発明の薄膜トランジスタの製造においては、Mo等の金属薄膜をエッチングしてソース・ドレイン電極、チャネル部を形成するフォトリソ工程も可能となる。
実施例1-3
平均粒径0.98μmの酸化インジウム粉及び平均粒径0.97μmの酸化アルミニウム粉を、表1に示す原子比Al/(Al+In)となるように秤量し、均一に微粉砕混合後、成形用バインダーを加えて造粒した。次に、この原料混合粉を金型へ均一に充填しコールドプレス機にてプレス圧140MPaで加圧成形した。このようにして得た成形体を焼結炉により表1に示す焼成温度及び焼成時間で焼成して、焼結体を製造した。
焼成雰囲気は昇温中は酸素雰囲気で、その他は大気中(雰囲気)であり、焼成は、昇温速度1℃/min、降温速度15℃/minで実施した。
尚、用いた原料酸化物粉末の平均粒径は、レーザー回折式粒度分布測定装置SALD-300V(島津製作所製)で測定し、平均粒径はメジアン径D50を採用した。
チャートを分析した結果、実施例1-3の焼結体には酸化インジウムのビックスバイト構造のみが観測された。当該結晶構造は、JCPDS(Joint Committee of Powder Diffraction Standards)カードで確認することができる。酸化インジウムのビックスバイト構造は、JCPDSカードNo.06-0416である。
装置:(株)リガク製Ultima-III
X線:Cu-Kα線(波長1.5406Å、グラファイトモノクロメータにて単色化)
2θ-θ反射法、連続スキャン(1.0°/分)
サンプリング間隔:0.02°
スリット DS、SS:2/3°、RS:0.6mm
装置名:JXA-8200(日本電子株式会社製)
加速電圧:15kV
照射電流:50nA
照射時間(1点当り):50mS
尚、上記異常放電の有無は、電圧変動をモニターし異常放電を検出することにより行った。具体的には、5分間の測定時間中に発生する電圧変動がスパッタ運転中の定常電圧の10%以上あった場合を異常放電とした。特にスパッタ運転中の定常電圧が0.1秒間に±10%変動する場合は、スパッタ放電の異常放電であるマイクロアークが発生しており、素子の歩留まりが低下し、量産化に適さないおそれがある。
尚、スパッタ条件は、スパッタ圧0.4Pa、DC出力100W、基板温度:室温であり、雰囲気ガスに添加した水素ガスは、ノジュールの発生を促進するためである。
ノジュールは、スパッタリング後のターゲット表面の変化を実体顕微鏡により50倍に拡大して観察し、視野3mm2中に発生した20μm以上のノジュールについて数平均を計測する方法を採用した。発生したノジュール数を表1に示す。
平均粒径0.98μmの酸化インジウム粉及び平均粒径0.97μmの酸化アルミニウム粉を表2に示す原子比Al/(Al+In)となるように秤量し、表2に示す焼成温度及び焼成時間で焼成した他は実施例1-3と同様にして焼結体及びターゲットを製造し、評価した。結果を表2に示す。
尚、比較例1は酸化インジウム粉のみを用いて焼結体及びターゲットを製造した。
酸化アルミニウムの代わりに、比較例4では平均粒径1.06μmの酸化イットリウム粉(Y2O3粉)を、比較例5では平均粒径1.02μmの酸化ホウ素粉(B2O3粉)を表2に示す原子比M(M+In)となるようにそれぞれ秤量し、表2に示す焼成温度及び焼成時間で焼成した他は実施例1-3と同様にして焼結体及びターゲットを製造し、評価した。結果を表2に示す。
実施例4
ガラス基板上及び厚み100nmの熱酸化膜(SiO2)付きシリコン基板上にそれぞれ実施例1で得られたターゲット(Al/(In+Al)=0.013)を用いてDCマグネトロンスパッタリング法により膜厚50nmの薄膜を成膜した。
スパッタリングは、背圧が1×10-4Paとなるまで真空排気したあと、アルゴン9.9sccm、水0.1sccm(水分圧:4.0×10-3Pa)流しながら、圧力を0.4Paに調整し、スパッタ出力100Wにて室温で行った。
また、アニール処理後の薄膜のキャリア濃度及び移動度をHall効果測定で評価したところ、キャリア濃度は6.98×1017cm-3であり、ホール移動度は24.5cm2/Vsであった。アニール処理後の薄膜の原子比が、用いたターゲットの原子比と同じであることも確認した。
ガラス基板上及び厚み100nmの熱酸化膜(SiO2)付きシリコン基板上にそれぞれ実施例2で得られたターゲット(Al/(In+Al)=0.027)を用いてDCマグネトロンスパッタリング法により膜厚50nmの薄膜を成膜した。
スパッタリングは、背圧が1×10-4Paとなるまで真空排気したあと、アルゴン9.9sccm、水0.1sccm(水分圧:4.0×10-3Pa)流しながら、圧力を0.4Paに調整し、スパッタ出力100Wにて室温で行った。
また、アニール処理後の薄膜のキャリア濃度及び移動度をHall効果測定で評価したところ、キャリア濃度は2.37×1017cm-3であり、ホール移動度は22.1cm2/Vsであった。
ガラス基板上及び厚み100nmの熱酸化膜(SiO2)付きシリコン基板上にそれぞれ実施例3で得られたターゲット(Al/(In+Al)=0.078)を用いてDCマグネトロンスパッタリング法により膜厚50nmの薄膜を成膜した。
スパッタリングは、背圧が1×10-4Paとなるまで真空排気したあと、アルゴン9.9sccm、水0.1sccm(水分圧:4.0×10-3Pa)流しながら、圧力を0.4Paに調整し、スパッタ出力100Wにて室温で行った。
また、アニール処理後の薄膜のキャリア濃度及び移動度をHall効果測定で評価したところ、キャリア濃度は5.88×1016cm-3であり、ホール移動度は18.8cm2/Vsであった。
ガラス基板上及び厚み100nmの熱酸化膜(SiO2)付きシリコン基板上にそれぞれ比較例3で得られたターゲット(Al/(In+Al)=0.23)を用いてDCマグネトロンスパッタリング法により膜厚50nmの薄膜を成膜した。
スパッタリングは、背圧が1×10-4Paとなるまで真空排気したあと、アルゴン9.9sccm、水0.1sccm(水分圧:4.0×10-3Pa)流しながら、圧力を0.4Paに調整し、スパッタ出力100Wにて室温で行った。
また、アニール処理後の薄膜のキャリア濃度及び移動度をHall効果測定で評価したところ、キャリア濃度は7.28×1016cm-3であり、ホール移動度は9.7cm2/Vsであり、実施例4~6の薄膜よりもホール移動度が顕著に劣っていることが分かる。
この明細書に記載の文献の内容を全てここに援用する。
Claims (8)
- インジウム及びアルミニウムの酸化物を含有し、
原子比Al/(Al+In)が0.01~0.08である酸化物焼結体。 - 平均粒径が1.2μm未満の酸化インジウム粉末、及び平均粒径が1.2μm未満の酸化アルミニウム粉末を、原子比Al/(Al+In)が0.01~0.08となるように混合して混合粉末を調製する工程、
前記混合粉末を成形して成形体を製造する工程、及び
前記成形体を1100℃~1550℃で8時間以上焼成する工程を含む請求項1に記載の酸化物焼結体の製造方法。 - 前記焼成を酸化ガス雰囲気中で行なう請求項2に記載の酸化物焼結体の製造方法。
- 請求項1に記載の酸化物焼結体を加工して得られるターゲット。
- 請求項4に記載のターゲットをスパッタリングして薄膜を成膜し、前記薄膜をアニールすることで得られる酸化物半導体薄膜であって、
原子比Al/(Al+In)が0.01~0.08であり、酸化インジウムのビックスバイト構造を有する酸化物半導体薄膜。 - 前記スパッタリングを水分圧5×10-4~7×10-2Paで行なう請求項5に記載の酸化物半導体薄膜。
- 請求項5又は6に記載の酸化物半導体薄膜をチャネル層として有する薄膜トランジスタ。
- 請求項7に記載の薄膜トランジスタを備えてなる表示装置。
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CN106986656A (zh) * | 2017-06-03 | 2017-07-28 | 嘉兴新耐建材有限公司 | 一种石灰窑用抗结皮耐磨预制砖 |
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TW201200612A (en) | 2012-01-01 |
US9153438B2 (en) | 2015-10-06 |
TWI535872B (zh) | 2016-06-01 |
CN102918003A (zh) | 2013-02-06 |
KR20130080011A (ko) | 2013-07-11 |
US20130082218A1 (en) | 2013-04-04 |
JP5689250B2 (ja) | 2015-03-25 |
JP2011249570A (ja) | 2011-12-08 |
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