US20150311071A1 - Sputtering target, oxide semiconductor thin film, and method for producing oxide semiconductor thin film - Google Patents

Sputtering target, oxide semiconductor thin film, and method for producing oxide semiconductor thin film Download PDF

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US20150311071A1
US20150311071A1 US14/414,850 US201314414850A US2015311071A1 US 20150311071 A1 US20150311071 A1 US 20150311071A1 US 201314414850 A US201314414850 A US 201314414850A US 2015311071 A1 US2015311071 A1 US 2015311071A1
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thin film
sputtering
oxide semiconductor
oxide
sputtering target
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Kazuaki Ebata
Mami Nishimura
Nozomi Tajima
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Idemitsu Kosan Co Ltd
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Idemitsu Kosan Co Ltd
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Assigned to IDEMITSU KOSAN CO., LTD. reassignment IDEMITSU KOSAN CO., LTD. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: TAJIMA, Nozomi, EBATA, KAZUAKI, NISHIMURA, MAMI
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    • C04B35/453—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zinc, tin, or bismuth oxides or solid solutions thereof with other oxides, e.g. zincates, stannates or bismuthates
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Definitions

  • the invention relates to a sputtering target, an oxide semiconductor thin film and a method for producing the same.
  • Field effect transistors such as a thin film transistor (TFT) are widely used as the unit electronic device of a semiconductor memory integrated circuit, a high frequency signal amplification device, a device for a liquid crystal drive, or the like, and they are electronic devices which are currently most widely put into practical use.
  • TFT thin film transistor
  • LCD liquid crystal display
  • EL electroluminescent display
  • FED field emission display
  • a silicon semiconductor compound As a material of a semiconductor layer (channel layer) which is a main component of a field effect transistor, a silicon semiconductor compound is used most widely. Generally, a silicon single crystal is used for the high frequency amplification device, the device for integrated circuits or the like which need high-speed operation. On the other hand, an amorphous silicon semiconductor (amorphous silicon) is used for a device for driving a liquid crystal in order to satisfy the demand for realizing a large-area display.
  • a thin film of amorphous silicon can be formed at relatively low temperatures.
  • the switching speed thereof is slow as compared with that of a crystalline thin film. Therefore, when it is used as a switching device that drives a display, it may be unable to follow the display of a high-speed animation.
  • amorphous silicon having a mobility of 0.5 to 1 cm 2 /Vs could be used in a liquid crystal television of which the resolution is VGA.
  • the resolution is equal to or more than SXGA, UXGA and QXGA, a mobility of 2 cm 2 /Vs or more is required.
  • the driving frequency is increased in order to improve the image quality, a further higher mobility is required.
  • a crystalline silicon-based thin film although it has a high mobility, there are problems that a large amount of energy and a large number of steps are required for the production, and that large-area film formation is difficult.
  • a silicon-based thin film is crystallized, a high temperature of 800° C. or more or laser annealing which needs expensive equipment is required.
  • the device configuration of a TFT is normally restricted to a top-gate configuration, and hence, reduction in production cost such as decrease in number of masks is difficult.
  • an oxide semiconductor thin film is formed by sputtering using a target (sputtering target) composed of an oxide sintered body.
  • a target formed of a homologous crystal structure compound such as In 2 Ga 2 ZnO 7 and InGaZnO 4 is known (Patent Documents 1, 2 and 3).
  • this target in order to increase the sintering density (relative density), it is required to conduct sintering in an oxidizing atmosphere. In this case, in order to reduce the resistance of the target, a reduction treatment at a high temperature is required to be conducted after sintering.
  • Patent Document 4 a thin film transistor that is obtained by using an amorphous oxide semiconductor film that does not contain gallium and is composed of indium oxide and zinc oxide has been proposed (Patent Document 4).
  • this thin film transistor has a problem that a normally-off operation of a TFT cannot be realized as long as the oxygen partial pressure at the time of film formation is increased.
  • Patent Documents 5 and 6 studies have been made on a sputtering target for forming a protective layer of an optical information recording medium, that is obtained by adding an additive element such as Ta, Y, Si or the like to an In 2 O 3 —SnO 2 —ZnO-based oxide composed mainly of tin oxide.
  • these targets have problems that they are not used for forming an oxide semiconductor, an agglomerate of an insulating material is likely to be formed easily, whereby the resistance is increased or abnormal discharge tends to occur easily.
  • Patent Document 1 JP-A-H8-245220
  • Patent Document 2 JP-A-2007-73312
  • Patent Document 3 WO2009/084537
  • Patent Document 4 WO2005/088726
  • Patent Document 5 WO2005/078152
  • Patent Document 6 WO2005/078153
  • An object of the invention is to provide a high-density and low-resistant sputtering target.
  • Another object of the invention is to provide a thin film transistor having a high field effect mobility and high reliability.
  • the following sputtering target or the like are provided.
  • In, Sn, Zn and Al are respectively the substance amount of the indium element, the tin element, the zinc element and the aluminum element in the sputtering target.
  • the sintering temperature is 1200° C. to 1650° C.
  • FIG. 1 is a view showing a sputtering apparatus used in one embodiment of the invention.
  • FIG. 2 is a view showing X-ray diffraction charts of a sintered body obtained in Example 1.
  • the sputtering target of the invention is composed of an oxide that comprises an indium element (In), a tin element (Sn), a zinc element (Zn) and an aluminum element (Al), and comprises a homologous structure compound represented by InAlO 3 (ZnO) m (m is 0.1 to 10).
  • the homologous crystal structure is a crystal formed of a long-period “natural superlattice” structure in which crystal layers of different substances are stacked. If the crystal period or the thickness of each thin film layer is on a nanometer level, a homologous structure compound can exhibit inherent characteristics that differ from the characteristics of a single substance or a mixed crystal in which the layers are uniformly mixed.
  • the relative density of the target can be increased.
  • the specific resistance of the target can be 6 m ⁇ cm or less, for example. Abnormal discharge can be suppressed when the target has a specific resistance of 5 m ⁇ cm or less.
  • RAO 3 As the oxide crystal having a homologous crystal structure, an oxide crystal represented by RAO 3 (MO m ) can be given.
  • R is a positive trivalent metal element.
  • In Ga, Al, Fe and B can be given.
  • A is a positive trivalent metal element that is different from R, and examples of which include Ga, Al and Fe.
  • M is a positive divalent metal element, and Zn and Mg can be given, for example.
  • R, A and M may be the same metal element or may be metal elements different from each other.
  • m is an integer, for example, and is preferably 0.1 to 10, more preferably 0.5 to 7, and further preferably 1 to 3.
  • the homologous structure compound represented by InAlO 3 ((ZnO) m may be a single substance or a mixture of two or more.
  • the homologous structure compound is one or more selected from a homologous structure compound represented by InAlZn 2 O 5 and a homologous structure compound represented by InAlZnO 4 .
  • Each of the homologous structure compound represented by InAlZn 2 O 5 and a homologous structure compound represented by InAlZnO 4 corresponds to a case where R is In, A is Al and M is Zn.
  • the homologous crystal structure in the target can be confirmed by X-ray diffraction.
  • X-ray diffraction For example, it can be confirmed by a fact that an X-ray diffraction pattern measured from powder obtained by pulverizing the target or an X-ray diffraction pattern measured directly from the target corresponds to an X-ray diffraction pattern of the crystal structure of the homologous phase assumed from the composition ratio.
  • the pattern is coincident with the crystal structure X-ray diffraction pattern of the homologous phase obtained from the JCPDS (Joint Committee of Powder Diffraction Standards).
  • the homologous crystal structure represented by InAlZnO 4 shows, in an X-ray diffraction, a peak pattern of No. 40-0258 of the data base of the JCPDS, or a similar (shifted) pattern.
  • the homologous crystal structure represented by InAlZn 2 O 5 shows a peak pattern of No. 40-0259 of the data base of the JCPDS or a similar (shifted) pattern.
  • the sputtering target of the invention preferably comprises a spinal structure compound represented by Zn 2 SnO 4 .
  • the spinal structure normally means AB 2 X 4 type or A 2 BX 4 type structure, and a compound having such a crystal structure is referred to as a spinal structure compound.
  • cations normally, oxygen
  • anions are present in part of the tetrahedral interstitial site or the octahedral interstitial site thereof.
  • a substitutional solid solution in which a part of atoms or ions in a crystal structure are replaced by other atoms and an interstitial solid solution in which other atoms are added to a position between lattices are included in a spinal structure compound.
  • Presence or absence of the spinel structure compound represented by Zn 2 SnO 4 in the sputtering target can be confirmed by X-ray diffraction.
  • the spinel structure compound represented by Zn 2 SnO 4 is a compound showing a peak pattern of No. 24-1470 of JCPDS database or a similar (shifted) peak pattern.
  • the sputtering target of the invention do not comprise a bixbyite structure compound represented by In 2 O 2 .
  • the bixbyite structure compound (or a C-type crystal structure of a rare-earth oxide) also refers to as a C-type rare-earth oxide or Mn 2 O 3 (I) type oxide.
  • Mn 2 O 3 (I) type oxide As stated in the “Technology of Transparent Conductive Film” (published by Ohmsha Ltd., edited by Japan Society for the Promotion of Science, transparent oxide/photoelectron material 166 committee, 1999) or the like, this compound has a chemical stoichiometric ratio of M 2 X 3 (M is a cation and X is an anion, which is normally an oxygen ion), and one unit cell is formed of 16 M 2 X 3 molecules and total 80 atoms (the number of M is 32 and the number of X is 48).
  • the bixbyite structure compound includes a substitutional solid solution in which a part of atoms or ions in a crystal structure are replaced by other atoms and an interstitial solid solution in which other atoms are added to a position between lattices are included in a bixbyite structure compound represented by In 2 O 3 .
  • Presence or absence of a bixbyite structure compound represented by In 2 O 2 , in a sputtering target can be confirmed by X-ray diffraction.
  • the bixbyite structure compound represented by In 2 O 3 shows a peak pattern of No. 06-0416 of JCPDS (Join(Committee on Powder Diffraction Standards) or a similar (shifted) pattern.
  • An oxide constituting the sputtering target of the invention containing an indium element (In), a tin element (Sn), a zinc element (Zn) and an aluminum element Al) satisfy the following atomic ratio.
  • the oxide satisfies the following atomic ratio, the relative density of the target can be 98% or more and the bulk resistance can be 5 m ⁇ cm or less.
  • In, Sn, Zn and Al are respectively the substance amount of the indium element, the tin element, the zinc element and the aluminum element in the sputtering target.
  • the bulk resistance value of the sputtering target may become high, resulting in impossibility in DC sputtering.
  • a bixbyte structure compound represented by In 2 O 3 may be formed in the target. If the target comprises a bixbyte compound represented by In 2 O 3 in addition to a homologous structure compound represented by lnAlZnO 4 , a homologous structure compound represented by InAlZn 2 O 5 and a spinal structure compound represented by Zn 2 SnO 4 , the sputtering speed varies depending on the crystal phase, and hence, parts remaining unremoved may be formed, whereby abnormal discharge may occur. Further, at the time of firing, abnormal particle growth may occur at a place where In 2 O 3 is agglomerated, voids may remain, and the density of the entire sintered body may not be improved.
  • the formula (1) is 0.10 ⁇ In/(In+Sn+Zn+Al) ⁇ 0.60, preferably 0.15 ⁇ Sn/(In+Sn+Zn+Al) ⁇ 0.50, and more preferably 0.20 ⁇ Zn/(In+Sn+Zn+Al) ⁇ 0.40.
  • the oxide density is not fully improved, and the bulk resistance of the target may become high.
  • the atomic ratio of the tin element exceeds 0.30, the solubility in a wet etchant of a thin film obtained from the target may be lowered, whereby wet etching may become difficult.
  • the formula (2) is 0.10 ⁇ Sn/(In+Sn+Zn+Al) ⁇ 0.30, preferably 0.05 ⁇ Sn/(In+Sn+Zn+Al) ⁇ 0.25, and further preferably 0.07 ⁇ Sn(In+Sn+Zn+Al) ⁇ 0.18.
  • the formula (3) is 0.10 ⁇ An/(In+Sn+Zn+Al) ⁇ 0.65, preferably 0.25 ⁇ Sn/(In+Sn+Zn+Al) ⁇ 0.60 and further preferably 0.40 ⁇ Sn/(In+Sn+Zn+Al) ⁇ 0.60.
  • the target resistance may not be fully lowered. If a channel layer of a TFT is formed by using a target, the reliability of a TFT may be deteriorated. On the other hand, if the atomic ratio of the aluminum element exceeds 0.30, Al 2 O 3 may be generated in the target, causing abnormal discharge.
  • the formula (4) is 0.01 ⁇ Sn/(In+Sn+Zn+Al) ⁇ 0.30, preferably 0.02 ⁇ Sn/(In+Sn+An+Al) ⁇ 0.25, and further preferably 0.02 ⁇ Sn(In+Sn+Zn+Al) ⁇ 0.15.
  • the atomic ratio of elements contained in the sintered body can be obtained by quantitatively analyzing the elements contained with Induction Coupled Plasma Atomic Emission Spectrometry (ICP-AES).
  • ICP-AES Induction Coupled Plasma Atomic Emission Spectrometry
  • each element contained in the sample absorbs thermal energy, and is excited, and the orbital electrons migrate from the ground state to the orbital at a high energy level.
  • the orbital electrons then migrate to the orbital at a lower energy level when about 10 ⁇ 7 to about 10 ⁇ 8 seconds has elapsed.
  • the difference in energy is emitted as light. Since the emitted light has an element-specific wavelength (spectral line), the presence or absence of each element can be determined based on the presence or absence of the spectral line (qualitative analysis).
  • the element concentration in the sample can be determined by comparison with a standard solution having a known concentration (quantitative analysis).
  • the content of each element is determined by quantitative analysis, and the atomic ratio of each element is calculated from the results.
  • the sputtering target may comprise inevitably mixed-in impurities other than In, Sn, Zn and Al as long as the effects of the invention are not impaired.
  • the sputtering target may substantially comprise only In, Sn, Zn and Al
  • the sputtering target used in the invention have a relative density of 98% or more. If an oxide semiconductor is deposited on a large-sized substrate (1G or more) with an increased sputtering output, it is preferred that the relative density be 98% or more.
  • Relative density is at least 98%, sputtering stable state is maintained.
  • a sputtering target is used having e relative density below 98%, blackening of the target surface or occurrence of abnormal discharge may be occurred.
  • the relative density is preferably 98.5% or more, with 99% or more being further preferable.
  • the relative density can be measured by the Archimedian method.
  • the relative density is preferably 100% or less. If the relative density exceeds 100%, metal particles may be generated in a sintered body or a lower oxide may be generated. Therefore, it is required to adjust strictly the amount of oxygen supplied at the time of film formation.
  • the density can be adjusted by a post treatment or the like such as a heat treatment in the reductive atmosphere after sintering.
  • a post treatment or the like such as a heat treatment in the reductive atmosphere after sintering.
  • an atmosphere such as argon, nitrogen and hydrogen, or an atmosphere of a mixture of these gases can be used.
  • the bulk specific resistance is preferably 5 m ⁇ cm or less, more preferably 3 m ⁇ cm or less. By a bulk specific resistance of 5 m ⁇ cm or less, abnormal discharge can be suppressed.
  • the bulk specific resistance mentioned above can be measured by a four probe method using a resistivity meter.
  • the maximum particle size of the crystal in the sintered body be 8 ⁇ m or less. If the crystal is grown to have a particle size exceeding 8 ⁇ m, nodules may hardly be generated.
  • the grinding speed differs depending on the direction of the crystal surface, whereby unevenness is generated on the target surface.
  • the size of this unevenness varies depending on the particle size of the crystal present in the sintered body. It is assumed that, and in the target formed of a sintered body having a large crystal particle size, a greater scale of unevenness occurs, and nodules are generated from this convex part.
  • the maximum particle size of the crystal of the sputtering target is obtained as follows. If the sputtering target has a circular shape, at five locations in total, i.e. the central point (one) and the points (four) which are on the two central lines crossing orthogonally at this central point and are middle between the central point and the peripheral part, or if the sputtering target has a square shape, at five locations in total, i.e. the central point (one) and middle points (four) between the central point and the corner of the diagonal line of the square, the maximum diameter is measured for the biggest particle observed within a 100- ⁇ m square. The maximum particle size is the average value of the particle size of the biggest particle present in each of the frames defined by the five locations. As for the particle size, the longer diameter of the crystal particle is measured. The crystal particles can be observed by the scanning electron microscopy (SEM).
  • the method for producing a sputtering target of the invention comprises the following two steps, for example:
  • In, Sn, Zn and Al are respectively the substance amount of the indium element, the tin element, the zinc element and the aluminum element.
  • the compound containing one or more element selected from In, Sn, Zn and Al a combination of indium oxide, tin oxide, zinc oxide and an aluminum metal, a combination of indium oxide, tin oxide, zinc oxide and aluminum oxide or the like can be mentioned.
  • the raw material compounds mentioned above be powder.
  • the raw material be a mixed powder of indium oxide, tin oxide, zinc oxide and aluminum oxide.
  • metal particles of aluminum may be present in the resulting sintered body.
  • metal particles on the target surface are molten during film formation and hence cannot be emitted from the target, resulting in a great difference between the composition of the film and the composition of the sintered body.
  • the average particle diameter of the raw material powder is preferably 0.1 ⁇ m to 1.2 ⁇ m, more preferably 0.1 ⁇ m to 1.0 ⁇ m.
  • the average particle diameter of the raw material powder can be measured by a laser diffraction particle size distribution measuring apparatus or the like.
  • an oxide containing In 2 O 3 powder having an average particle diameter of 0.1 ⁇ m to 1.2 ⁇ m, SnO 2 powder having an average particle diameter of 0.1 ⁇ m to 1.2 ⁇ m, ZnO powder having an average particle diameter of 0.1 ⁇ m to 1.2 ⁇ m and Al 2 O 3 powder having an average particle diameter of 0.1 ⁇ m to 1.2 ⁇ m is used as the raw material powder. They may be contained in an amount ratio that satisfies the above-mentioned formulas (1) to (4).
  • the method for mixing and forming of the raw material compound is not particularly restricted, and a known method can be used.
  • a water-based solvent is compounded with raw material powders including indium oxide powder, tin oxide powder, zinc oxide powder and aluminum oxide powder, and the resulting slurry is mixed for 12 hours or more.
  • the mixture is subjected to solid-liquid separation, dried and granulated, and the granulated product is then put in a mold and formed, whereby a formed body is obtained.
  • a wet or dry ball mill, a vibration mill, a beads mill or the like can be used.
  • the most preferable method is a beads mill mixing method since it can pulverize the aggregate efficiently for a short period of time and can realize a favorable dispersed state of additives.
  • the mixing time is preferably 15 hours or more, more preferably 19 hours or more. If the mixing time is insufficient, a high-resistant compound such as Al 2 O 3 may be generated in the oxide sintered body finally obtained.
  • the mixing time varies depending on the size of the apparatus used and the amount of slurry to be treated. However, the mixing time is controlled appropriately such that the particle distribution in the slurry becomes uniform, i.e. all of the particles have a particle size of 1 ⁇ m or less.
  • an arbitral amount of a binder is added, and mixing may be conducted simultaneously with the addition of the binder.
  • the binder polyvinyl alcohol, vinyl acetate or the like can be used.
  • quick dry granulation For granulation of a raw material powder slurry obtained by mixing, it is preferable to use quick dry granulation.
  • a spray dryer As the apparatus for quick dry granulation, a spray dryer is widely used. Specific drying conditions are determined according to conditions such as the concentration of slurry to be dried, the temperature of hot air used for drying and the amount of wind. For actually conducting the quick dry granulation, it is required to obtain optimum conditions in advance.
  • the granulated powder can normally be formed to a formed body at a pressure of 1.2 ton/cm 2 more by means of a mold press or cold isostatic pressing (CIP).
  • CIP cold isostatic pressing
  • the resulting formed body is sintered at 1200 to 1650° C. for 10 to 50 hours to obtain a sintered body.
  • the sintering temperature is preferably 1350 to 1600° C., more preferably 1400 to 1600° C., and further preferably 1450 to 1600° C.
  • the sintering time is preferably 12 to 40 hours, more preferably 13 to 30 hours.
  • the sintering temperature is lower than 1200° C. and the sintering time is shorter than 10 hours, Al 2 O 3 or the like may be formed within the target, thereby causing abnormal discharge.
  • the calcination temperature exceeds 1650° C. or the calcination time exceeds 50 hours, an increase in average crystal diameter due to significant crystal particle growth or generation of large voids may occur, thereby causing lowering in strength of a sintered body or occurrence of abnormal discharge.
  • a pressure sintering method such as hot pressing, oxygen pressurization and hot isostatic pressing or the like can be used.
  • atmospheric sintering pressing In respect of a decrease in production cost, possibility of mass production and easiness in production of a large-sized sintered body, it is preferable to use atmospheric sintering pressing.
  • a formed body is sintered in the air or the oxidizing gas atmosphere.
  • a formed body is sintered in the oxidizing gas atmosphere.
  • the oxidizing gas atmosphere is preferably an oxygen gas atmosphere. It suffices that the oxygen gas atmosphere be an atmosphere having an oxygen concentration of 10 to 100 vol %, for example.
  • the density of the sintered body can be further increased by introducing an oxygen gas atmosphere during the temperature-elevating step.
  • the temperature-elevating rate at the time of sintering it is preferred that the temperature-elevating rate be 0.1 to 2° C./min in a temperature range of from 800° C. to a sintering temperature (1200 to 1650° C.).
  • a temperature range of from 800° C. and higher is a range where sintering proceeds most quickly. If the temperature-elevating rate in this temperature range is less than 0.1° C./min, growth of crystal particles becomes significant, whereby an increase in density may not be attained. On the other hand, if the temperature-elevating rate is higher than 2° C./min, Al 2 O 3 or the like may be deposited within the target.
  • the temperature-elevating rate from 800° C. to a sintering temperature is preferably 0.1 to 1.3° C./min, more preferably 0.1 to 1.1° C./min.
  • a reduction step may be further provided, if necessary.
  • a method using a reductive gas, a reduction treatment by vacuum calcination, a reduction treatment by calcination in an inert gas or the like can be given, for example.
  • the temperature at the time of the above-mentioned reduction treatment is normally 100 to 800° C., preferably 200 to 800° C.
  • the reduction treatment is conducted normally for 0.01 to 10 hours, preferably 0.05 to 5 hours.
  • a water-based solvent is compounded with raw material powders containing mixed powder of indium oxide power, tin oxide power, zinc oxide powder and aluminum oxide powder to obtain a slum/. Thereafter, the slurry is mixed for 12 hours or longer, and is subjected to solid-liquid separation, dried and granulated. Subsequently, the granulated product is put in a mold and formed. Then, the resulting formed body is sintered at 1200 to 1650° C. for 10 to 50 hours with a temperature-elevating rate in a temperature range of from 800° C. to the sintering temperature being 0.1 to 2° C./min, whereby a sintered body can be obtained.
  • the sputtering target of the invention can be obtained. Specifically, by grinding the sintered body into a shape suited to be mounted in a sputtering apparatus, a sputtering target material is obtained. Then, the sputtering target material is bonded to a backing plate, whereby a sputtering target can be obtained.
  • the sintered body is ground by means of a surface grinder to allow the surface roughness Ra to be 0.5 ⁇ m or less. Further, the sputtering surface of the target material may be subjected to mirror finishing, thereby allowing the average surface roughness thereof Ra to be 1000 ⁇ or less.
  • polishing techniques such as mechanical polishing, chemical polishing, mechano-chemical polishing (combination of mechanical polishing and chemical polishing) or the like may be used.
  • it can be obtained by polishing by means of a fixed abrasive polisher (polishing liquid: water) to attain a roughness of #2000 or more, or can be obtained by a process in which, after lapping by a free abrasive lap (polisher: SiC paste or the like), lapping is conducted by using diamond paste as a polisher instead of the SiC paste.
  • polishing liquid polisher
  • SiC paste free abrasive lap
  • the target material may be finished by means of a #200 to #10,000 diamond wheel, particularly preferably by means of a #400 to #5,000 diamond wheel. If a diamond wheel with a mesh size of smaller than #200 or larger than #10,000 is used, the target material may be broken easily.
  • the surface roughness Ra of the target material be 0.5 ⁇ m or less and that the grinding surface have no directivity. If Ra is 0.5 ⁇ m or larger or the grinding surface has directivity, occurrence of abnormal discharge generation of particles may be occurred.
  • the thus processed target material may be subjected to a cleaning treatment.
  • a cleaning treatment For cleaning, air blowing, washing with running water or the like can be used.
  • foreign matters When foreign matters are removed by air blowing, foreign matters can be removed more effectively by air intake by means of a dust collector from the side opposite from the nozzle.
  • ultrasonic cleaning or the like can also be conducted.
  • ultrasonic cleaning it is effective to conduct multiplex oscillation within a frequency range of 25 to 300 KHz.
  • the thickness of the target material is normally 2 to 20 mm, preferably 3 to 12 mm, and particularly preferably 4 to 6 mm.
  • a sputtering target By bonding the target material obtained in the manner as mentioned above to a backing plate, a sputtering target can be obtained.
  • a plurality of target materials may be provided in a single backing plate to be used as a substantially single target.
  • the sputtering target of the invention can have a relative density of 98% or more and a bulk resistance of 5 m ⁇ cm or less. When sputtering is conducted, occurrence of abnormal discharge can be suppressed.
  • the sputtering target of the invention can form a high-quality oxide semiconductor thin film efficiently and inexpensively and in an energy-saving manner.
  • the oxide semiconductor thin film of the invention can be obtained.
  • the oxide semiconductor thin film of the invention is composed of in zinc, aluminum and oxygen and preferably satisfies the following atomic ratios (1) to (4):
  • In, Sn, Zn and Al are respectively the substance amount of the indium element, the tin element, the zinc element and the aluminum element.
  • the amount of the In element is less than 0.10, the bulk resistance of the sputtering target is increased, and as a result, DC sputtering becomes impossible.
  • the amount of the In element exceeds 0.60, if the formed film is applied to the channel layer of a TFT, reliability may be lowered.
  • the amount of the Sn element is less than 0.01, the target resistance is increased, and film formation may not be stabilized due to occurrence of abnormal discharge during sputtering.
  • the amount of an Sn element exceeds 0.30, solubility of the resulting thin film in a wet etchant is lowered, whereby wet etching may become difficult.
  • the resulting film may not be a stable amorphous film.
  • the amount of the Zn element exceeds 0.65, since the dissolution speed of the resulting thin film in a wet etchant is too high, resulting in difficulty in wet etching.
  • the oxygen partial pressure during film formation may be increased. Since the Al element is bonded to oxygen strongly, it can lower the oxygen partial pressure during film formation. Further, when a channel layer is formed and applied to a TFT, reliability may be lowered. On the other hand, if the amount of the Al element exceeds 0.30, Al 2 O 3 may be generated in the target, abnormal discharge may occur at the time of film formation by sputtering, leading to unstable film formation.
  • the carrier concentration of the oxide semiconductor thin film is normally 10 19 /cm 3 or less, preferably 10 13 to 10 18 /cm 3 , further preferably 10 14 to 10 18 /cm 3 , and particularly preferably 10 15 to 10 18 /cm 3 .
  • the carrier concentration of the oxide layer is larger than 10 19 cm ⁇ 3 , current leakage may not occur easily when a device such as a thin film transistor is fabricated. Further, since the transistor may become normally-on or may not have a large on-off ratio, good transistor performance may not be exhibited. Further, if a carrier concentration is less than 10 13 cm ⁇ 3 , the device can be driven as a TFT due to small numbers of carriers.
  • the carrier concentration of the oxide semiconductor thin film can be measured by the hail-effect measurement.
  • the sputtering target of the invention has a high conductivity. Accordingly, a DC sputtering method having a high film forming speed can be applied.
  • the RF sputtering, the AC sputtering, the pulse DC sputtering can also be applied, and sputtering free from abnormal discharge is possible.
  • the oxide semiconductor thin film can also be prepared by the deposition method, the sputtering method, the ion plating method, the pulse laser deposition method or the like can be prepared.
  • the sputtering gas As the sputtering gas (atmosphere), a mixed gas of atoms of a rare gas such as argon and an oxidizing gas can be used.
  • a mixed gas composed of rare gas atoms, and one or more molecules selected from water molecules, oxygen molecules and nitrous oxide molecules is preferable. It is more preferred that the sputtering gas be a mixed gas that contains rare metal atoms and at least water molecules.
  • the oxygen partial pressure at the time of film formation by sputtering is preferably 0% or more and less than 40%.
  • a thin film formed under the conditions in which the oxygen partial pressure is 40% or more may have a significantly decreased carrier concentration as less than 10 13 cm ⁇ 3 .
  • the oxygen partial pressure is preferably 0% to 30% and particularly preferably 0% to 20%.
  • the partial pressure ratio of water contained in a sputtering gas (atmosphere) at the time of depositing an oxide thin film in the invention i.e. [H 2 O]/([H 2 O]+[rare gas]+[other molecules], is preferably 0.1 to 25%.
  • the water partial pressure in the atmosphere at the time of sputtering is more preferably 0.7 to 13%, with 1 to 6% being particularly preferable.
  • the substrate temperature at the time of film formation by sputtering is preferably 25 to 120° C., further preferably 25 to 100° C., and particularly preferably 25 to 90° C. If the substrate temperature at the time of film formation is higher than 120° C., oxygen or the like introduced at the time of film formation may be incorporated in a small amount, and the carrier concentration of the thin film after heating may exceed 10 19 cm 3 . Further, if the substrate temperature at the time of film formation is lower than 25° C., the density of the thin film may be lowered, and as a result, mobility of a TFT may be lowered.
  • the oxide thin film obtained by sputtering be further subjected to an annealing treatment by retaining at 150 to 500° C. for 15 minutes to 5 hours.
  • the annealing treatment temperature after film formation is more preferably 200° C. or more and 450° C. or less, further preferably 250° C. or more and 350° C. or less.
  • the heating atmosphere is not particularly restricted. In respect of carrier control properties, the air atmosphere or the oxygen-circulating atmosphere is preferable.
  • a lamp annealing apparatus in the presence or absence of oxygen, a lamp annealing apparatus, a laser annealing apparatus, a thermal plasma apparatus, a hot air heating apparatus, a contact heating apparatus or the like can be used.
  • the distance between the target and the substrate at the time of sputtering is preferably 1 to 15 cm in a direction perpendicular to the film formation surface of the substrate, with 2 to 8 cm being further preferable. If this distance is less than 1 cm, the kinetic energy of particles of target-constituting elements which arrive the substrate may become large, good film properties may not be obtained, and in-plane distribution of the film thickness and the electric characteristics may occur. If the interval between the target and the substrate exceeds 15 cm, the kinetic energy of particles of target-constituting elements which arrive the substrate may be too small, and a dense film may not be obtained, and as a result, good semiconductor properties may not be attained.
  • film formation be conducted by sputtering in an atmosphere having a magnetic field intensity of 300 to 1500 gausses. If the magnetic field intensity is less than 300 gausses, since the plasma density may decrease, sputtering may not be conducted if the sputtering target has a high resistance. On the other hand, if the magnetic field intensity exceeds 1500 gausses, the film thickness and the electric characteristics of the film may be poor-controlled.
  • the pressure of a gas atmosphere is preferably 0.1 to 3.0 Pa, further preferably 0.1 to 1.5 Pa, with 0.1 to 1.0 Pa being particularly preferable. If the sputtering pressure exceeds 3.0 Pa, the mean free path of sputtering particles may be shortened, thereby lowering the density of a thin film. If the sputtering pressure is less than 0.1 Pa, fine crystals may be formed in a film during film formation. Meanwhile, the sputtering pressure is the total pressure in the system at the start of sputtering after rare gas atoms (e.g. argon), water molecules, oxygen molecules or the like are introduced.
  • rare gas atoms e.g. argon
  • a cyan (CN)-containing solution can be used.
  • the cyan (CN)-containing solution used for cleaning it is preferable to use the following.
  • Hydrogen cyanide (HCN) is dissolved in water or ultrapure water, or at least one solvent selected from an alcohol-based solvent, a ketone-based solvent, a nitrile-based solvent, an aromatic hydrocarbon-based solvent, carbon tetrachloride, an ether-based solvent, an aliphatic alkane-based solvent or a mixed solvent of these. Further, the resulting solution is diluted to a predetermined concentration, followed by adjusting the hydrogen ion concentration index (the so-called pH value) in the solution with an ammonium aqueous solution or the like to a range of preferably 9 to 14.
  • the content of cyan (CN) is 100 ppm or less, for example, preferably 1 ppm to 10 ppm. It is preferred that the cyan-containing solution having a hydrogen ion concentration index (pH) of 9 to 14 be heated, and the surface of the semiconductor substrate or the gate insulating film be subjected to a cleaning treatment at a prescribed temperature of 50° C. or less, preferably 30° C. to 40° C.
  • cyanide ions By using an aqueous HCN solution, cyanide ions (CN ⁇ ) is reacted with copper on the surface of the substrate to form [Cu(CN) 2 ]—, whereby contamination by copper is removed.
  • the complex ion forming capability of CN ⁇ ions is significantly large. Even in an aqueous solution of HCN having a very low concentration, CN ⁇ ions effectively react, thereby enabling removal of contamination by copper.
  • the formation of an oxide semiconductor thin film may be conducted by the following AC sputtering.
  • Substrates are transported in sequence to positions opposing to 3 or more targets arranged in parallel with a prescribed interval in a vacuum chamber. Then, a negative potential and a positive potential are applied alternately from an AC power source to each of the targets, whereby plasma is caused to be generated on the target.
  • film formation is conducted by applying at least one output from an AC power source between 2 or more targets connected divergently, while switching the target to which a potential is applied. That is, at least one output from the AC power source is connected divergently to 2 or more targets respectively, whereby film formation is conducted while applying differential potentials to the adjacent targets.
  • an oxide semiconductor thin film is formed by AC sputtering, it is preferred that sputtering be conducted in an atmosphere of a mixed gas containing rare gas atoms, and one or more molecules selected from water molecules, oxygen molecules and nitrous oxide molecules, for example. It is particularly preferred that sputtering be conducted in an atmosphere of a mixed atom containing water molecules.
  • the AC sputtering apparatus disclosed in JP-A-2005-290550 specifically has a vacuum chamber, a substrate holder arranged within the vacuum chamber and a sputtering source arranged at a position opposing to this substrate holder.
  • FIG. 1 shows essential parts of a sputtering source of the AC sputtering apparatus.
  • the sputtering source has a plurality of sputtering parts, which respectively have plate-like targets 31 a to 31 f. Assuming that the surface to be sputtered of each target 31 a to 31 f is a sputtering surface, the sputtering parts are arranged such that the sputtering surfaces are on the same plane.
  • Targets 31 a to 31 f are formed in a long and narrow form having a longitudinal direction, and they have the same shape.
  • the targets are arranged such that the edge parts (side surface) in the longitudinal direction of the sputtering surface are arranged in parallel with a prescribed interval. Accordingly, the side surfaces of the adjacent targets 31 a to 31 f are in parallel.
  • AC power sources 17 a to 17 c are arranged.
  • one terminal is connected to one electrode of the adjacent two electrodes, and the other terminal is connected to the other electrode.
  • the two terminals of each AC power source 17 a to 17 c output voltages differing in polarity (positive and negative), and the targets 31 a to 31 f are fitted in close contact with the electrode, whereby, to adjacent two targets 31 a to 31 f, an alternate voltage differing in polarity is applied from the AC power sources 17 a to 17 c. Therefore, among the adjacent targets 31 a to 31 f, if one is set in a positive potential, the other is set in a negative potential.
  • Each magnetic field forming means 40 a to 40 f has a long and narrow ring-like magnet having an approximately same size as that of the outer circumference of the targets 31 a to 31 f, and a bar-like magnet which is shorter than the length of the ring-like magnet.
  • Each ring-like magnet is arranged at the position right behind one corresponding targets 31 a to 31 f such that the ring-like magnets are arranged in parallel with the longitudinal direction of the targets 31 a to 31 f.
  • the ring-like magnets are arranged with the same interval as that for the targets 31 a to 31 f.
  • the AC power density when an oxide target is used in AC sputtering is preferably 3 W/cm 2 or more and 20 W/cm 2 or less. If the power density is less than 3 W/cm 2 , the film-forming speed is slow, and is not economically advantageous in respect of production. A power density exceeding 20 W/cm 2 may cause breakage of the target. A more preferable power density is 3 W/cm 2 to 15 W/cm 2 .
  • the frequency of the AC sputtering is preferably in the range of 10 kHz to 1 MHz. If the frequency is lower than 10 kHz, noise problems occur If the frequency exceeds 1 MHz, sputtering may be conducted in other places than the desired target position due to excessively wide scattering of plasma, whereby uniformity may be deteriorated.
  • a more preferable AC sputtering frequency is 20 kHz to 500 kHz.
  • Conditions or the like at the time of sputtering other than those mentioned above may be appropriately selected from the conditions given above.
  • the above-mentioned oxide thin film can be used in a thin film transistor. It can be used particularly preferably as a channel layer.
  • a thin film transistor using the oxide semiconductor thin film of the invention as a channel layer has a high mobility of a field effect mobility of 15 cm 2 /Vs or more and a high reliability.
  • the thickness of the channel layer in the thin film transistor of the invention is normally 10 to 300 nm, preferably 20 to 250 nm, more preferably 30 to 200 nm, further preferably 35 to 120 nm, and particularly preferably 40 to 80 nm. If the thickness of the channel layer is less than 10 nm, due to uniformity of the film thickness when the film is formed to have a large area, the properties of a TFT fabricated may become un-uniform within the plane. A film thickness exceeding 300 nm is not preferable, since the film formation time may be prolonged, making industrial application impossible.
  • the channel layer of the thin film transistor of the invention may be partially crystallized at least in a region overlapping the gate electrode.
  • the “crystallized” means that crystal particles grow from the amorphous state to the state in which crystal nucleus is generated or the state in which crystal nucleus has been generated.
  • reduction resistance relative to the plasma process CVD process, or the like
  • the crystallized region can be confirmed by an electron diffraction image of a transmission electron microscope (TEM: Transmission Electron Microscope).
  • the channel layer in the thin film transistor of the invention is normally used in the N-type region.
  • the channel layer in combination with various P-type semiconductors such as a P-type Si-based semiconductor, a P-type oxide semiconductor and a P-type organic semiconductor, the channel layer can be used in various semiconductor devices such as a PN junction transistor.
  • the protective film in the thin film transistor of the invention comprise at least SiN x .
  • SiN x is capable of forming a dense film, and hence has an advantage that it has significant effects of preventing deterioration of a TFT.
  • the protective film may comprise, in addition to SiNx, an oxide such as SiO 2 , 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 2 O, Sc 2 O 3 , Y 2 O 3 , HfO 2 , CaHfO 3 , PbTiO 3 , BaTa 2 O 6 , Sm 2 O 3 , SrTiO 3 or AlN.
  • an oxide such as SiO 2 , 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 2 O, Sc 2 O 3 , Y 2 O 3 , HfO 2 , CaHfO 3 , PbTiO 3 , BaTa 2 O 6 , Sm 2 O 3 , SrTiO 3 or AlN.
  • the oxide thin film of the invention that comprises an indium element (in), a tin element (Sn), a zinc element (Zn) and an aluminum element (Al), since it contains Al, resistance to reduction by the CVD process is improved. As a result, the back channel side is hardly reduced by a process in which a protective film is prepared, whereby SiN, can be used as a protective film.
  • the channel layer be subjected to an ozone treatment, an oxygen plasma treatment, a nitrogen dioxide plasma treatment or a nitrous oxide plasma treatment.
  • an oxygen plasma treatment a nitrogen dioxide plasma treatment or a nitrous oxide plasma treatment.
  • Such a treatment may be conducted at any time as long as it is after the formation of a channel layer and before the formation of a protective film. However, it is desirable that the treatment be conducted immediately before the formation of a protective film. By conducting such a pretreatment, generation of oxygen deficiency in the channel layer can be suppressed.
  • the threshold voltage may be shifted, resulting in lowering of reliability of a TFT.
  • an oxygen plasma treatment or a nitrous oxide plasma treatment the In—OH bonding in the thin film structure is stabilized, whereby diffusion of hydrogen in the oxide semiconductor film can be suppressed.
  • an insulating film with a thickness of several nm may be formed on the surface of an oxide semiconductor film.
  • the thin film transistor normally comprises a substrate, a gate electrode, a gate insulating layer, an organic semiconductor layer (channel layer), a source electrode and a drain electrode.
  • the channel layer is as mentioned above.
  • a known material can be used for the substrate.
  • a material which is generally used can be arbitrary selected. Specifically, a compound such as SiO 2 , SiN x , 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 2 O, Sc 2 O 3 , Y 2 O 3 , HfO 2 , CaHfO 3 , PbTiO 3 , BaTa 2 O 6 , SrTiO 2 , Sm 2 O 3 , AlN or the like can be used, for example.
  • a compound such as SiO 2 , SiN x , 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 2 O, Sc 2 O 3 , Y 2 O 3 , HfO 2 , CaHfO 3 , PbTiO 3 , BaTa 2
  • SO 2 , SiN x , Al 2 O 3 , Y 2 O 3 , HfO 2 and CaHfO 3 are preferable, with SiO 2 , SiN x , HfO 2 and Al 2 O 3 being more preferable.
  • the gate insulating film can be formed by the plasma CVD (Chemical Vapor Deposition) method, for example.
  • a gate insulating film is formed by the plasma CVD method and a channel layer is formed thereon, hydrogen in the gate insulating film diffuses in the channel layer, and as a result, deterioration of film quality of the channel layer or lowering of reliability of a TFT may be caused.
  • the gate insulating film be subjected to an ozone treatment, an oxygen plasma treatment, a nitrogen dioxide plasma treatment or a nitrous oxide plasma treatment before the formation of a channel layer.
  • the number of oxygen atoms of these oxides does not necessarily coincide with the stoichiometric ratio.
  • SiO 2 or SiO x may be used.
  • the gate insulting 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.
  • the gate insulating film is preferably polycrystalline or amorphous from the viewpoint of easiness of industrial production.
  • each electrode in the thin film transistor i.e. a drain electrode, a source electrode and a gate electrode
  • materials which are generally used can be arbitrarily selected.
  • transparent electrodes such as ITO, IZO, ZnO, SnO 2 or the like
  • a metal electrode such as Al, Ag, Cu, Cr, Ni, Mo, Au, Ti, and Ta or an alloy metal electrode containing these metals can be used.
  • the S value can be derived from a reciprocal of the slope of a graph of Log(Id)-Vg obtained from the results of transfer characteristics.
  • the unit of the S value is V/decade, and a smaller S value is preferable.
  • the S value is preferably 0.8 V/decade or less, more preferably 0.5V/dec or less, further preferably 0.3 V/dec or less, and 0.2 V/dec or less is particularly preferable. If the S value is 0.8 V/dec or less, the driving voltage is reduced, and consumption power may be able to be reduced. In particular, if the thin film transistor is used in an organic EL display, since it is driven by DC driving, it is preferable to allow the S value to be 0.3V/dec or less in view of a significant decrease in consumption power.
  • the S value is a value indicating the sharpness of rising of the drain current from the off-state to the on-state when the gate voltage of a transistor is increased from the off-state.
  • the S value is defined by the following formula. As shown by the following formula, the S value is an increase in gate voltage when the drain current increases by one digit (10 times).
  • the oxide thin film composed of In, Sn, Zn and Al that is applied to the channel layer can be subjected to wet etching in an organic acid-based etching liquid (for example, oxalic acid-etching liquid), and is hardly dissolved in an inorganic acid-based wet etching liquid (for example, a mixed acid wet etching liquid of phosphoric acid/nitric acid/acetic acid: PAN).
  • an organic acid-based etching liquid for example, oxalic acid-etching liquid
  • an inorganic acid-based wet etching liquid for example, a mixed acid wet etching liquid of phosphoric acid/nitric acid/acetic acid: PAN.
  • the selection ratio of wet etching to Mo (molybdenum) or Al (aluminum) or the like used in the electrode is large. Therefore, by using the oxide thin film composed of In, Sn, Zn and Al in a channel layer, a channel-etch type thin film transistor can be
  • Each of the drain electrode, the source electrode and the gate electrode may have a multi-layer structure in which two or more different conductive layers are stacked.
  • the electrodes since the source/drain electrodes are required to be used in low-resistance wiring, the electrodes may be used by sandwiching a good conductor such as Al and Cu between metals having good adhesiveness such as Ti and Mo.
  • the thin film transistor of the invention can be applied to various integrated circuits such as a field effect transistor, a logical circuit, a memory circuit and a differential amplifier circuit. Further, in addition to a field effect transistor, it can be applied to a static induction transistor, a Schottky barrier transistor, a Schottky diode and a resistance element.
  • a known configuration such as a bottom-gate configuration, a bottom-contact configuration and a top-contact configuration can be used without restrictions.
  • a bottom-gate configuration is advantageous since high performance can be obtained as compared with a thin film transistor comprising amorphous silicon and ZnO.
  • the bottom-gate configuration is preferable since the number of masks at the time of production can be decreased easily and the production cost for application such as a large-sized display or the like can be reduced easily.
  • the thin film transistor of the invention can preferably be used as a display.
  • a channel-etch type bottom-gate thin film transistor For use in a large-sized display, a channel-etch type bottom-gate thin film transistor is particularly preferable.
  • a channel-etch type bottom-gate thin film transistor can produce a panel for a display at a low cost since the number of photo-masks used in photolithography is small.
  • a channel-etch type thin film transistor having a bottom-gate configuration and a channel-etch type thin film transistor having a top-contact configuration are particularly preferable since they have excellent properties such as mobility and can be industrialized easily.
  • the median size D50 was employed as an average particle size for the following oxide powders.
  • the average particle size was measured by a laser diffraction particle size analyzer SALD-300V (manufactured by Shimadzu Corporation).
  • Indium oxide powder average particle size 0.98 ⁇ m
  • Tin oxide powder average particle size 0.08 ⁇ m
  • Zinc oxide powder average particle size 0.96 ⁇ m
  • Aluminum oxide powder average particle size 0.98 ⁇ m
  • the above-mentioned powders were weighed such that the atomic ratio shown in Table 1 was attained. They were finely pulverized and mixed uniformly and then granulated by adding a binder for forming. Subsequently, the mixed powder of the raw materials was filled in the mold uniformly and press-formed at a pressing pressure of 140 MPa in a cold press apparatus.
  • the formed body thus obtained was sintered in a sintering furnace at a temperature-elevation rate of temperature (from 800° C. to a sintering temperature) at a sintering temperature for a sintering time shown in Table 1 to produce a sintered body.
  • a temperature-elevation rate of temperature from 800° C. to a sintering temperature
  • a sintering temperature for a sintering time shown in Table 1 to produce a sintered body.
  • the temperature-decreasing rate was 15° C./min.
  • the relative density of the sintered body obtained was measured by the Archimedean method.
  • the sintered bodies of Examples 1 to 8 were confirmed to have a relative density of 98% or more.
  • the bulk specific resistance (conductivity) of the sintered body obtained was measured by means of a resistivity meter (Loresta, manufactured by Mitsubishi Chemical Analytech Co., Ltd.) in accordance with the four-probe measurement (JIS R 1837). The results are shown in Table 1. As shown in Table 1, the bulk specific resistances of the sintered bodies of Examples 1 to 8 were 5 m ⁇ cm or less.
  • the crystal structure of the sintered body obtained was determined by means of an X-ray diffraction (XRD) meter.
  • XRD X-ray diffraction
  • An X-ray diffraction chart of the sintered body obtained in Example 1 is shown in FIG. 2 .
  • the sintered bodies of Examples 1 to 8 the dispersion of Sn and Al in the sintered body obtained by the electron probe microanalyzer (EPMA) measurement was checked, 8 ⁇ m or larger-sized aggregation of Sn or Al was not observed. As a result, the sintered bodies of Examples 1 to 3 were found to be significantly excellent in dispersivity and homogeneousness.
  • EPMA electron probe microanalyzer
  • the EPMA measurement was conducted under the following conditions.
  • the surface of the sintered bodies obtained in Examples 1 to 8 was ground by means of a surface grinder. The sides thereof were cut using a diamond cutter. The sintered bodies thus shaped were bonded to a backing plate, thereby to obtain sputtering targets each having a diameter of 4 inches. Further, in Examples 1, 4 and 6, 6 targets each having a width of 200 mm, a length of 1700 mm and a thickness of 10 mm were fabricated for AC sputtering film-forming.
  • a sputtering target having a diameter of 4 inches obtained was mounted in a DC sputtering apparatus.
  • a mixed gas obtained by adding H 2 O gas to argon gas at a partial pressure of 2% was used as the atmosphere.
  • a 10 kWh continuous sputtering was conducted at a DC power of 400 W with the sputtering pressure being 0.4 Pa and the substrate temperature being room temperature.
  • the variation in voltage during the sputtering was stored in data logger to confirm the presence or absence of abnormal discharge. The results are shown in Table 1.
  • abnormal discharge is defined by the case where the voltage variation generated for a measurement time of 5 minutes is 10% or more of the working voltage during sputtering operation.
  • microarcs which are abnormal discharge during sputtering, may generate, thereby lowering the yield of a device. Accordingly, they may be unsuitable for mass production.
  • Sputtering was conducted continuously for 40 hours by using a 4-inch-diameter sputtering target obtained with the atmosphere being a mixed gas obtained by adding a hydrogen gas to argon gas at a partial pressure ratio of 3% to confirm the presence or absence of nodule generation.
  • the atmosphere being a mixed gas obtained by adding a hydrogen gas to argon gas at a partial pressure ratio of 3% to confirm the presence or absence of nodule generation.
  • the conditions at the time of the sputtering include a sputtering pressure of 0.4 Pa, a DC power of 100 W and a substrate temperature of room temperature.
  • the hydrogen gas was added to the atmosphere gas in order to promote nodule generation.
  • nodules For evaluation of nodules, the following method was employed. The change in the target surface after sputtering was observed at a magnification of 50 times by means of a stereomicroscope. The number average of nodules having a size of 20 ⁇ m or larger generated in the visual field of 3 mm 2 was calculated. Table 1 shows the number of nodules generated.
  • Sintered bodies and sputtering targets were produced and evaluated in the same manner as in Examples 1 to 8, except that the raw material powders were mixed according to the atomic ratio shown in Table 1, and sintered at a temperature-elevating rate (from 890° C. to a sintering temperature), at a sintering temperature and for a sintering time as shown in Table 1. The results are shown in Table 1.
  • Example 1 0.25 0.15 0.55 0.05 0.15 1400 15
  • Example 2 0.25 0.15 0.50 0.10 0.15 1400 15
  • Example 3 0.30 0.10 0.50 0.10 0.15 1450 15
  • Example 4 0.30 0.20 0.45 0.05 0.15 1450 20
  • Example 5 0.20 0.20 0.50 0.10 0.10 1450 15
  • Example 6 0.25 0.10 0.60 0.05 0.15 1450 15
  • Example 7 0.25 0.15 0.50 0.10 0.10 1450 15
  • Example 8 0.30 0.15 0.40 0.15 0.10 1450 15
  • Comp. 0.50 0.05 0.10 0.35 5.5 1200 8 Ex. 1 Comp. 0.50 0.10 0.05 0.35 5.5 1200 8 Ex.
  • Example 1 InAlZn 2 O 5 99.2 1.8 None 0 Zn 2 SnO 4
  • Example 2 InAlZn 2 O 5 98.8 2.6 None 0 InAlZnO 4 Zn 2 SnO 4
  • Example 3 InAlZn 2 O 5 99.5 1.8 None 0 InAlZnO 4 Zn 2 SnO 4
  • Example 4 InAlZn 2 O 5 99.0 2.1 None 0 Zn 2 SnO 4
  • Example 5 InAlZn 2 O 5 98.8 1.5 None 0 Zn 2 SnO 4
  • Example 6 InAlZn 2 O 5 99.1 2.6 None 0 Zn 2 SnO 4
  • Example 7 InAlZn 2 O 5 99.0 2.1 None 0 Zn 2 SnO 4
  • Example 8 InAlZn 2 O 5 98.5 1.4 None 0 InAlZnO 4
  • the 4-inch targets produced in Examples 1 to 8 and shown in Tables 2 and 3 were mounted in a magnetron sputtering apparatus, and slide glass (#1737, manufactured by Corning Inc.) was installed as a substrate.
  • slide glass #1737, manufactured by Corning Inc.
  • a 50 nm-thick amorphous film was formed on the slide glass under the following conditions.
  • an Ar gas, an O 2 gas and a H 2 O gas were introduced at partial pressures (%) shown in Tables 2 and 3.
  • the substrate on which an amorphous film was formed was heated in an atmosphere at 300° C. for 60 minutes, whereby an oxide semiconductor thin film was formed.
  • Substrate temperature 25° C.
  • Atmospheric gas Ar gas, O 2 gas, H 2 O gas (for partial pressure, see Table 2)
  • a glass substrate on which an oxide semiconductor film was formed was set in a Resi Test 8300 (manufactured by TOY0 Corporation), and the Hall effect was evaluated at room temperature. Further, by the ICP-AES analysis, it was confirmed that the atomic ratio of each element contained in the oxide thin film was the same as that of the sputtering target.
  • the crystal structure was examined by means of an X-ray diffraction measurement apparatus (Ultima-III, manufactured by Rigaku Corporation).
  • the measuring conditions of the X-ray diffraction measurement are as follows.
  • a conductive silicon substrate provided with a 100 nm-thick thermally oxidized film was used.
  • the thermally oxidized film functioned as a gate insulating film and the conductive silicon part functioned as a gate electrode.
  • a film was formed by sputtering under the conditions shown in Tables 2 and 3, whereby a 50 nm-thick amorphous thin film was fabricated.
  • OFPR #300 manufactured by Tokyo Ohka Kogyo Co., Ltd.
  • Coating, pre-baking (60° C., 5 minutes) and exposure were conducted.
  • post-baking 120° C., 5 minutes
  • etching with oxalic acid, and patterning into a desired shape were conducted. Thereafter, the film was subjected to a heat treatment at 300° C. for 60 minutes in a hot-air oven (annealing treatment).
  • Mo 100 nm
  • source/drain electrodes were patterned by the lift-off process in a desired shape.
  • Tables 2 and 3 as a pretreatment before forming a protective film, an oxide semiconductor film was subjected to a nitrous oxide plasma treatment. Further, SiO x was formed into a film by the plasma CVD (PECVD) method to obtain a protective film. A contact hole was formed by using hydrofluoric acid, whereby a thin film transistor was fabricated.
  • the field effect mobility ( ⁇ ) was calculated from the linear mobility, and defined as the maximum value of Vg- ⁇ .
  • oxide semiconductor thin films and thin film transistors were fabricated and evaluated in the same manner as in Examples 9 to 16 in accordance with the sputtering, heating (annealing) conditions and a pretreatment for forming a protective film shown in Table 3. The results are shown in Table 3.
  • the devices of Comparative Examples 3 and 4 had a field effect mobility of less than 15 cm 2 /Vs, which was significantly lower than those in Examples 9 to 16.
  • the threshold voltage was varied by 1V or more, showing that it underwent significant deterioration of characteristics.
  • Example 10 Example 11
  • the oxide semiconductor thin film and the thin film transistor were fabricated and evaluated in the same manner as in Examples 9 to 16. The results are shown in Table 4. In Examples 17 to 19, AC sputtering was conducted instead of DC sputtering to form a film.
  • Example 17 6 targets 31 a to 31 f (each having a width of 200 mm, a length of 1700 mm and a thickness of 10 mm) fabricated in Example 1 were used. These targets 31 a to 31 f were arranged parallel to the direction of the width of a substrate such that they remote from each other with an interval of 2 mm. The width of the magnetic field forming means 40 a to 40 f was 200 mm as in the case of targets 31 a to 31 f.
  • the glass substrate on which a thin film had been formed and subjected to a heat treatment in the air at 300° C. for 60 minutes (in the atmosphere).
  • the thin film was cut into a size of 1 cm 2 , and then subjected to a Hall effect treatment by the four probe method.
  • the carrier concentration was 2.62 ⁇ 10 17 cm ⁇ 3 , indicating that the film became a sufficient semiconductor.
  • an XRD measurement it was confirmed that the oxide thin film was amorphous immediately after the thin film deposition, and was still amorphous after allowing it to stand in the air at 300° C. for 60 minutes.
  • the ICP-AES analysis it was confirmed that the atomic ratio of each element contained in the oxide thin film was the same as that of the sputtering target.
  • the oxide semiconductor thin film and thin film transistor were fabricated and evaluated in the same manner as in Examples 17 to 19, except that, instead of the targets used in Examples 1, 4 and 6, the target prepared in Comparative Example 1 was used. The results are shown in Table 4.
  • the device of Comparative Example 5 had a field effect mobility of less than 15 cm 2 /Vs, which was significantly lower than those in Examples 17 to 19.
  • a conductive silicon substrate with a thermally oxidized film with a thickness of 100 nm was used as the substrate.
  • the thermally oxidized film functioned as a gate insulating film, and the conductive silicon part functioned as a gate electrode.
  • the conductive silicon substrate with a thermally oxidized film was washed with an aqueous HCN solution (washing liquid) having an extremely low concentration (1 ppm) and a pH of 10. The washing was conducted while setting the temperature to 30° C.
  • the targets prepared in Examples 1 to 8, 1 and 2 were used.
  • a 50 nm-thick amorphous film was formed by sputtering under the sputtering and annealing conditions shown in Tables 5 and 6.
  • OFPR #800 manufactured by Tokyo Ohka Kogyo Ltd.
  • Coating, pre-baking (80° C., 5 minutes) and exposure were conducted.
  • post-baking 120° C., 5 minutes
  • etching with oxalic acid, and patterning into a desired shape were conducted.
  • the film was subjected to a heat treatment at 450° C. for 60 minutes in a hot-air oven (annealing treatment).
  • the heating treatment annealing treatment was conducted at 300° C. for 60 minutes in a hot-air oven.
  • Mo 200 nm
  • the source/drain electrode was patterned into a desired shape by channel etching.
  • a nitrous oxide plasma treatment was conducted for an oxide semiconductor film.
  • An SiO x was formed into a film by the plasma CVD (PECVD) method to obtain a protective film.
  • a contact hole was formed by using hydrofluoric acid, whereby a back-channel etch type thin film transistor was fabricated.
  • HF-2100 field emission-type transmission electron microscope manufactured by Hitachi, Ltd.
  • a cross-sectional TEM analysis was conducted for the channel layer of the devices in Examples 20 to 26. No diffraction pattern was observed in the front channel side, showing that it was amorphous. A diffraction pattern was observed in part of the back channel side, showing that a crystallized region was present in the back channel side. On the other hand, as for the devices in Examples 27 to 29, no diffraction patterns were observed in both of the front channel side and the back channel side, showing that it was amorphous.
  • the field effect mobility ( ⁇ ) was calculated from the linear mobility, and defined as the maximum value of Vg- ⁇ .
  • Comparative Examples 6 and 7 a conductive silicon substrate provided with a thermally oxidized film was used as in the case of Examples 20 to 29. However, in Comparative Examples 6 and 7, washing with an aqueous HCN solution (washing solution) was not conducted.
  • the back channel etch type thin film transistors of Comparative Examples 6 and 7 had a field effect mobility of less than 15 cm 2 /Vs, that was significantly lower than the back channel etch type thin film transistors in Examples 20 to 29.
  • Example 20 Example 21
  • Example 22 Example 23
  • Example 26 Example 27
  • the thin film transistor obtained by using the sputtering target of the invention can be used as a display, in particular, as a large-area display.

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