WO2011061938A1 - 長期成膜時の安定性に優れたIn-Ga-Zn-O系酸化物焼結体スパッタリングターゲット - Google Patents
長期成膜時の安定性に優れたIn-Ga-Zn-O系酸化物焼結体スパッタリングターゲット Download PDFInfo
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- WO2011061938A1 WO2011061938A1 PCT/JP2010/006761 JP2010006761W WO2011061938A1 WO 2011061938 A1 WO2011061938 A1 WO 2011061938A1 JP 2010006761 W JP2010006761 W JP 2010006761W WO 2011061938 A1 WO2011061938 A1 WO 2011061938A1
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Definitions
- the present invention relates to a sputtering target for producing an oxide thin film such as an oxide semiconductor or a transparent conductive film, particularly for producing a thin film transistor.
- An amorphous oxide film made of indium oxide and zinc oxide, or made of indium oxide, zinc oxide and gallium oxide has visible light transmittance and wide electrical characteristics from conductors, semiconductors to insulators. Attention has been paid to transparent conductive films and semiconductor films (used for thin film transistors and the like).
- the oxide film As a method for forming the oxide film, there are physical film formation such as sputtering, pulse laser deposition (PLD), and vapor deposition, and chemical film formation such as a sol-gel method. As a method for uniformly forming a film, physical film formation such as a sputtering method has been mainly studied.
- an oxide thin film is formed by physical film formation such as sputtering
- a target made of an oxide sintered body is used in order to form a film uniformly, stably and efficiently (at a high film formation rate). It is common.
- oxide film for example, an oxide film made of indium oxide, zinc oxide, or gallium oxide can be given.
- a target mainly a sputtering target
- a known crystal type composition such as InGaZnO 4 , In 2 Ga 2 ZnO 7 or a composition close to that is known. Is mainly considered.
- Patent Document 1 discloses a target including a homologous structure of InGaZnO 4 (InGaO 3 (ZnO)).
- Patent Document 2 discusses a production method that does not generate a highly insulating Ga 2 O 3 crystal phase.
- Patent Documents 3 and 4 disclose a sputtering target mainly composed of ZnO. However, when only a target for an optical recording medium or a transparent electrode is studied, a thin film transistor is formed using such a target. The effect on transistor characteristics has not been studied.
- Patent Document 5 discusses the development of a target utilizing the characteristics of a mixture such as a target composed of a mixture of a hexagonal layered compound of InGaZnO 4 and a spinel structure of ZnGa 2 O 4 . However, in these examinations, examination of the properties of the target surface and internal crystal forms, etc., and matching these crystal forms are not considered.
- An object of the present invention is to provide a sputtering target that is excellent in stability of characteristics of a thin film obtained when film formation is performed over a long period of time.
- the instability of the characteristics of the thin film when the film is formed for a long time is caused by the property of the target (specific resistance, etc.) by continuing the sputtering for a long time. I found out that it was to change. Furthermore, when a sputtering target composed of indium oxide, zinc oxide and gallium oxide is formed for a long period of time, a change in crystal form (change in crystal type) occurs on the surface subjected to sputtering on the surface. I found out that it is the cause of.
- the molded body having a large thickness is heated at a slow speed to produce a sintered body, and the surface is sufficiently ground. It has been found that this can be solved by using a target and adopting conditions for generating an appropriate crystal form for each composition.
- the film is formed for a long time.
- the film formation rate did not change much even if the process was performed, and the change in characteristics of TFTs produced using the thin film obtained was successfully suppressed, and the present invention was completed. It has also been found that the use of the present invention reduces the difference between the composition of the target and the thin film, and improves the problem that the Ga content ratio of the thin film becomes extremely smaller than the Ga content ratio of the target.
- the manufacturing method of the following sputtering targets and sputtering targets is provided.
- a sputtering target comprising an oxide sintered body in which the crystal types of the surface and internal compounds are substantially the same.
- the ratio R1 / R2 of the specific resistance (R1) on the surface of the oxide sintered body and the specific resistance (R2) in the deep part t / 2 mm (t is the average thickness of the sputtering target) from the surface is 0.
- the sputtering target according to 4 above which has a crystal structure having an X-ray diffraction peak of Cuk ⁇ rays at 56.5 ° to 59.5 ° and satisfies the composition ratio of the region 4. 8).
- the substantially identical crystal type includes a spinel crystal structure represented by ZnGa 2 O 4 and a bixbite crystal structure represented by In 2 O 3 , and satisfies the composition ratio of the region 1 or region 3. 4.
- the method for producing a sputtering target according to any one of 4, 5, 6, and 8, comprising the following steps (a) to (e): (A) A step of preparing a mixture by mixing raw material compound powders, (B) forming the mixture to prepare a molded body having a thickness of 6.0 mm or more; (C) a step of heating the atmosphere at a heating rate of 3 ° C./min or less, (D) a step of further sintering the heated body at 1280 ° C. to 1520 ° C. for 2 hours to 96 hours to obtain a sintered body having a thickness of 5.5 mm or more, (E) Grinding the surface of the sintered body by 0.25 mm or more. 6.
- the method for producing a sputtering target according to 5 above which comprises the following steps (a) to (e): (A) A step of preparing a mixture by mixing raw material compound powders, (B) forming the mixture to prepare a molded body having a thickness of 6.0 mm or more; (C) a step of heating the atmosphere at a heating rate of 3 ° C./min or less, (D) a step of further sintering the temperature-increased molded body at 1350 ° C. to 1540 ° C. for 2 hours to 36 hours to obtain a sintered body having a thickness of 5.5 mm or more; (E) Grinding the surface of the sintered body by 0.25 mm or more. 8.
- the method for producing a sputtering target according to 8 above comprising the following steps (f) to (i): (F) mixing the raw material compound powder to prepare a mixture; (G) forming the mixture to prepare a molded body; (H) a step of heating the atmosphere at a heating rate of 10 ° C./min or less, (I) A step of further sintering the temperature-increased compact at 1100 ° C. to 1350 ° C. for 4 hours to 96 hours.
- the present invention it is possible to provide a sputtering target that is excellent in stability of characteristics of a thin film obtained when film formation is performed over a long period of time. According to the present invention, stable thin film transistor characteristics can be obtained even when film formation is performed over a long period of time.
- FIG. 1 It is a schematic diagram showing a structure of a channel stopper type thin film transistor (inverse stagger type thin film transistor) according to the present invention.
- the sputtering target of the present invention (hereinafter referred to as the target of the present invention) is composed of an oxide sintered body containing In, Zn, and Ga and having substantially the same crystal type of the surface and the inner compound. It is characterized by.
- substantially means that the types of crystal types identified when the surface and the surface cut into the inside are measured by X-ray diffraction measurement (XRD) may be the same.
- the crystal form of the target surface and the internal compound are cut at t / 2 mm from the surface, and the crystal form of the surface compound and t /
- the crystal form of the compound at a depth of 2 mm is determined by analysis by X-ray diffraction measurement (XRD).
- the crystal structure of the surface of the sputtering target can be confirmed from the X-ray diffraction pattern obtained by directly measuring the target surface by X-ray diffraction.
- the crystal structure of the deep part of the sputtering target can be confirmed from the obtained X-ray diffraction pattern by cutting the target horizontally in the plane and measuring the obtained cut surface directly by X-ray diffraction.
- the target cutting method is, for example, as follows. Apparatus: Maruto Co., Ltd. Million-Cutter 2 MC-503N Condition: Diamond blade ⁇ 200mm procedure: 1. Heat the absorption plate (alumina plate) and apply Adfix (adhesive manufactured by Marto) on the top surface. 2. After placing the target, fix the target by quenching with water. 3. Set the absorption plate on the device and cut the target. 4). After that, repeat steps 1 to 3 so that an arbitrary cutting surface is obtained.
- Apparatus Maruto Co., Ltd. Million-Cutter 2 MC-503N Condition: Diamond blade ⁇ 200mm procedure: 1. Heat the absorption plate (alumina plate) and apply Adfix (adhesive manufactured by Marto) on the top surface. 2. After placing the target, fix the target by quenching with water. 3. Set the absorption plate on the device and cut the target. 4). After that, repeat steps 1 to 3 so that an arbitrary cutting surface is obtained.
- the measurement conditions of X-ray diffraction are as follows, for example.
- Crystal type can be specified by checking with JCPDS card for those registered in JCPDS (Joint Committee of Powder Diffraction Standards) card.
- oxygen may be excessive or insufficient (oxygen deficiency) (may be shifted according to the stoichiometric ratio) or oxygen deficiency. It is preferable to have If the oxygen is excessive, the resistance may be too high when the target is used.
- the target of the present invention preferably has substantially the same peak intensity ratio when it contains two or more crystal types.
- the comparison of the peak intensity ratio is performed by the ratio of the maximum peak heights of the respective crystal types.
- the ratio of the maximum peak heights is compared, and if the difference is ⁇ 30% or less, it is judged that they are almost the same.
- the difference is more preferably ⁇ 15% or less, particularly preferably ⁇ 5% or less. It can be expected that the smaller the difference in the ratio of the maximum peak heights, the less the variation in the properties of the thin film obtained when used over a long period of time.
- the target of the present invention may contain a metal element other than the above-described In, Ga, Zn, for example, Sn, Ge, Si, Ti, Zr, and Hf, as long as the effects of the present invention are not impaired.
- the metal element contained in the target does not include elements other than impurities, which are inevitably included depending on the raw material and the manufacturing process, and only In, Ga and Zn, or only In, Ga, Zn and Sn. It may be.
- Both the crystal grain diameter on the surface and the crystal grain diameter at a depth of t / 2 mm from the surface are preferably 20 ⁇ m or less, more preferably 10 ⁇ m or less, and particularly preferably 5 ⁇ m or less.
- the ratio R1 / R2 of the specific resistance (R1) on the surface of the oxide sintered body and the specific resistance (R2) at a depth of t / 2 mm from the surface is 0.4 to 2.5. Preferably there is.
- R1 / R2 is preferably 0.4 or more and 2.5 or less, more preferably 0.5 or more and 2 or less, and particularly preferably 0.67 or more and 1.5 or less.
- R1 / R2 is less than 0.4 or more than 2.5, the properties (specific resistance, etc.) of the target change depending on when the target is used and when it is consumed over a long period of time. There is a risk of instability such as a change in speed or a change in the characteristics of the manufactured TFT.
- the composition ratio (atomic ratio) of In, Zn, and Ga of the oxide sintered body satisfies any of the following regions 1 to 6.
- a more preferable range of each region is as follows. Region 1 Ga / (In + Ga + Zn) ⁇ 0.45 0.58 ⁇ In / (In + Zn) ⁇ 0.80 In / (In + Ga) ⁇ 0.56 Region 2 Ga / (In + Ga + Zn) ⁇ 0.40 0.35 ⁇ In / (In + Zn) ⁇ 0.58 In / (In + Ga) ⁇ 0.58 Region 3 0.20 ⁇ Ga / (In + Ga + Zn) 0.60 ⁇ In / (In + Zn) ⁇ 0.85 0.60 ⁇ In / (In + Ga) Region 4 0.09 ⁇ Ga / (In + Ga + Zn) ⁇ 0.15 0.35 ⁇ In / (In + Zn) ⁇ 0.48 0.58 ⁇ In / (In + Ga) Region 5 0.09 ⁇ Ga / (In + Ga + Zn) ⁇ 0.20 0.53 ⁇ In / (In + Zn) ⁇ 0.75 Region 6 0.17 ⁇ Ga / (In + Ga
- Region 1 A TFT having a small photocurrent can be manufactured.
- a TFT having a high resistance to mixed acid can be manufactured.
- a target made of a substantially single crystal type (In 2 Ga 2 ZnO 7 ) can be manufactured.
- the crystal form of In 2 Ga 2 ZnO 7 can be generated by adjusting the production conditions such as the sintering temperature or by containing a small amount of dopant such as Sn.
- an oxide sintered body in which a crystal type other than the crystal type of In 2 Ga 2 ZnO 7 is not confirmed by XRD can be generated.
- conductivity can be increased by a layered structure.
- the crystal types of In 2 O 3 and ZnGa 2 O 4 can be included by adjusting the production conditions such as the sintering temperature.
- the crystal types of In 2 O 3 and ZnGa 2 O 4 it is easy to generate oxygen vacancies in In 2 O 3 without performing heat treatment in a reducing atmosphere, and the specific resistance can be reduced.
- the grinding amount is small, or it is easy to match the crystal types of the surface and the center without grinding. This seems to be because this crystal form is stable at a relatively low temperature.
- Region 2 A TFT with a small photocurrent can be manufactured.
- a target made of a substantially single crystal type (InGaZnO 4 ) can be manufactured.
- Region 3 A TFT having a slightly high mobility and a slightly small S value can be produced. When a TFT is produced, the photocurrent is small.
- region 3 by adjusting the production conditions such as the sintering temperature, In 2 O 3 Crystal forms can be included. By having a crystal form of In 2 O 3, without performing heat treatment in a reducing atmosphere becomes easy to generate the oxygen defects in the In 2 O 3, it is possible to lower the resistivity.
- Region 4 Fabrication of TFT with high mobility and small S value is possible. Fabrication of a target composed of a substantially single crystal type is possible. Reducing the specific resistance of the target is easy. By adjusting the conditions, it is possible to produce a target consisting essentially of a single crystal type. By being substantially single, the uniformity of the target is improved. In addition, conductivity is improved.
- Region 5 TFT having very high mobility and low S value can be manufactured. It is easy to reduce the specific resistance of the target.
- 2 ⁇ 7.0 ° to 8.4 °, 30.6 ° to 32.
- a target including the represented crystal form can be manufactured. This combination of crystal types facilitates generation of oxygen vacancies in In 2 O 3 without performing heat treatment in a reducing atmosphere, and can reduce the specific resistance.
- the sputtering target having the composition of the region 5 is suitable for obtaining a thin film transistor with high mobility in which a semiconductor layer is thinned.
- Region 6 TFT with slightly higher mobility and lower S value can be fabricated (Photocurrent, mixed acid resistance, and moisture resistance are better than those in Region 4)
- 2 ⁇ 7.0 ° to 8.4 °, 30.6 ° to 32.0 °, 33.8 ° to 35.8 °, 53.5 ° to 56.5 ° and 56.5 °
- a target including a crystal structure having an X-ray diffraction peak of Cuk ⁇ rays at ⁇ 59.5 ° and a crystal type represented by InGaZnO 4 can be manufactured. The conductivity is improved by the homologous structure.
- the photocurrent can be expected to decrease as Ga / (In + Zn + Ga) is larger than 0 and larger.
- the improvement in mobility can be expected as In / (In + Zn) is 0.20 or more and is larger. Moreover, it can be expected that the smaller the In / (In + Zn) is 0.80 or less, the easier it is to adjust normally-off.
- regions 1 and 2 having a large amount of Ga when film formation is performed by sputtering, changes in film formation rate and carrier density are relatively sensitive to oxygen partial pressure, so slight fluctuations and unevenness can be obtained. The uniformity of the thin film characteristics may be disturbed or the reproducibility may be reduced.
- the regions 3 to 6 are preferable, and the regions 4 and 5 are particularly preferable.
- substantially the same crystal type may consist of only one type of crystal type.
- the one type of crystal type has a homologous crystal structure represented by In 2 Ga 2 ZnO 7 and satisfy the composition ratio of the region 1.
- the crystal structure represented by In 2 Ga 2 ZnO 7 (or (InGaO 3 ) 2 ZnO) showing a (YbFeO 3 ) 2 FeO type crystal structure is called a “hexagonal layered compound” or “crystal structure of a homologous phase”.
- the crystal cycle or thickness of each thin film layer is on the order of nanometers, depending on the combination of the chemical composition of these layers and the thickness of the layers, it differs from the properties of a single substance or a mixed crystal in which each layer is uniformly mixed. Unique characteristics can be obtained.
- the crystal structure of the homologous phase is such that, for example, the X-ray diffraction pattern measured directly from the pulverized target, the cut piece or the target itself matches the crystal structure X-ray diffraction pattern of the homologous phase assumed from the composition ratio. It can be confirmed from. Specifically, it can be confirmed from the coincidence with the crystal structure X-ray diffraction pattern of the homologous phase obtained from a JCPDS (Joint Committee of Powder Diffraction Standards) card.
- the crystal structure represented by In 2 Ga 2 ZnO 7 is JCPDS card no. 38-1097.
- This crystal type can be easily obtained by including Sn (tin) in the composition of region 1 in the following composition ratio (atomic ratio). 0.005 ⁇ Sn / (In + Ga + Zn + Sn) ⁇ 0.10
- the range of the Sn content is more preferably as follows. 0.01 ⁇ Sn / (In + Ga + Zn + Sn) ⁇ 0.05
- the sintering temperature is preferably 1350 ° C. to 1540 ° C., more preferably 1380 to 1500 ° C.
- one type of crystal type has a homologous crystal structure represented by InGaO 3 (ZnO) and satisfy the composition ratio of the region 2 or the region 3.
- the crystal structure represented by InGaO 3 (ZnO) m (m is an integer of 1 to 20) is also a “hexagonal layered compound” or “a crystal structure of a homologous phase”.
- the crystal structure represented by InGaO 3 (ZnO) is JCPDS card no. 38-1104.
- This crystal type oxide crystal is a new crystal that has not been confirmed so far, and is not present in the JCPDS (Joint Committee of Powder Diffraction Standards) card.
- the X-ray diffraction chart of this oxide crystal shows a crystal structure represented by InGaO 3 (ZnO) 2 (JCPDS: 40-0252) and a crystal represented by In 2 O 3 (ZnO) 2 (JCPDS: 20-1442). Similar to structure.
- the oxide of the present invention has a peak peculiar to InGaO 3 (ZnO) 2 (the peak in the region A) and a peak peculiar to In 2 O 3 (ZnO) 2 (the peaks in the regions D and E).
- InGaO 3 (ZnO) 2 and In 2 O 3 (ZnO) 2 have peaks that are not observed (the region B). Therefore, the oxide of the present invention is different from InGaO 3 (ZnO) 2 and In 2 O 3 (ZnO) 2 .
- Condition 2 One of the diffraction peaks observed at 2 ⁇ of 30.6 ° to 32.0 ° (region B) and 33.8 ° to 35.8 ° (region C) is the main peak, and the other is the sub peak. It is.
- the main peak refers to the highest peak of the crystalline XRD pattern
- the sub peak refers to the second peak.
- the substantially same crystal type may be composed of two or more crystal types.
- the substantially same crystal type includes a spinel crystal structure represented by ZnGa 2 O 3 and a bixbite crystal structure represented by In 2 O 3 , and the region 1 or region 3 described above. It is preferable that the composition ratio is satisfied.
- the oxygen content of the tissue having a large amount of In is lower than the oxygen content of the other surrounding parts.
- the oxygen content of each tissue can be confirmed by a composition distribution using an electron probe microanalyzer (EPMA).
- the lattice constant a of the bixbyite structure represented by In 2 O 3 is preferably 10.14 or less, more preferably 10.10 or less, and particularly preferably 10.08 or less.
- the lattice constant a is obtained by XRD fitting. If the lattice constant is small, it can be expected that the specific resistance can be lowered by improving the mobility.
- This crystal type (including spinel crystal structure and bixbite crystal structure) can be expected to be obtained by sintering at 1100 ° C. to 1350 ° C. with the composition of region 1 or region 3.
- this crystal form can be generated, the types of crystal forms on the surface and in the deep part, even when the average thickness of the oxide sintered body is less than 5.5 mm or the surface grinding of the sintered body is less than 0.3 mm May be able to produce sputtering targets that are substantially the same.
- the oxygen content of the tissue having a large amount of In is lower than the oxygen content of the other surrounding parts.
- the oxygen content of each tissue can be confirmed by a composition distribution using an electron probe microanalyzer (EPMA).
- the lattice constant a of the bixbyite structure represented by In 2 O 3 is preferably 10.14 or less, more preferably 10.10 or less, and particularly preferably 10.08 or less.
- the lattice constant a is obtained by XRD fitting. If the lattice constant is small, it can be expected that the specific resistance can be lowered by improving the mobility.
- the first production method of the present invention includes the following steps (a) to (e).
- substantially the same crystal type consists of only one type of crystal, and the one type of crystal type is represented by In 2 Ga 2 ZnO 7.
- a target having a homologous crystal structure and satisfying the composition ratio of the region 1 a target having a homologous crystal structure in which one type of crystal type is represented by InGaO 3 (ZnO) and satisfying the composition ratio of the region 2
- the average thickness of the molded body is usually 6.0 mm or more, preferably 8 mm or more. If it is 6.0 mm or more, in-plane temperature unevenness is reduced, and it can be expected that variations in the types of crystal types on the surface and in the deep part are less likely to occur.
- the heating rate is usually 3.0 ° C./min or less, preferably 2.5 ° C./min or less, and particularly preferably 1.5 ° C./min or less.
- the lower limit of the temperature rising rate is about 0.3 ° C./min. If it is slower than 0.3 ° C./min, the sintering time may be excessively increased and the cost may increase. If the rate of temperature rise is more than 3 ° C./min, the types of crystal types on the surface and in the deep part may fluctuate. This is presumably because temperature unevenness occurs in the thickness direction of the target when the temperature is raised.
- the sintering temperature is usually from 1280 ° C to 1520 ° C, preferably from 1300 ° C to 1500 ° C.
- the sintering time is usually 2 hours to 96 hours, preferably 4 hours to 48 hours, and more preferably 6 hours to 24 hours.
- the grinding depth is usually 0.25 mm or more, preferably 0.3 mm or more, more preferably 0.5 mm or more, and particularly preferably 2 mm or more. If it is less than 0.25 mm, there is a possibility that the fluctuation part of the crystal structure near the surface cannot be removed sufficiently.
- the second production method of the present invention includes the following steps (a) to (e).
- substantially the same crystal type comprises one type of crystal type, and the one type of crystal type is represented by In 2 Ga 2 ZnO 7. This is useful for producing a target having a homologous crystal structure and satisfying the composition ratio of the region 1.
- the sintering temperature is usually more than 1350 ° C. and not more than 1540 ° C., preferably 1380 to 1510 ° C., more preferably 1400 to 1490 ° C.
- the sintering temperature is 1350 ° C. or lower or exceeds 1540 ° C., there is a possibility that a crystal type other than the above-described crystal type (homologous crystal structure represented by In 2 Ga 2 ZnO 7 ) may be obtained.
- the sintering time is usually 2 hours or more and 36 hours or less, preferably 4 to 24 hours, more preferably 8 to 12 hours.
- the sintering time exceeds 36 hours, there is a possibility that a crystal type other than the above-described crystal type (homologous crystal structure represented by In 2 Ga 2 ZnO 7 ) may be obtained.
- the third production method of the present invention is characterized by including the following steps (f) to (i).
- a spinel crystal structure represented by ZnGa 2 O 3 and a bixbite crystal structure represented by In 2 O 3 are substantially identical among the targets of the present invention.
- a sputtering target satisfying the composition ratio of the region 1 or the region 3 is useful.
- the heating rate is usually 10 ° C./min or less, preferably 6 ° C./min or less, more preferably 3 ° C./min or less. If the rate of temperature rise exceeds 10 ° C./min, properties such as the surface portion and the internal crystal form may change, or cracks may occur in the target. In addition, the lower limit of the temperature rising rate is about 0.3 ° C./min.
- the sintering temperature is usually 1100 ° C. or higher and 1350 ° C. or lower, and preferably 1200 ° C. or higher and 1300 ° C. or lower. If it is less than 1100 ° C., the relative density may not be increased, and it may take time for sintering.
- the temperature is higher than 1350 ° C., other crystal types generated at high temperature are generated, and the above crystal types (spinel crystal structure represented by ZnGa 2 O 3 and bixbite crystal structure represented by In 2 O 3 ) are obtained. There is a risk that it cannot be obtained stably.
- the sintering time is usually 4 hours to 96 hours, preferably 4 hours to 48 hours, and more preferably 6 hours to 24 hours. If it is less than 4 hours, the relative density may not increase. If it is 96 hours or longer, part of the composition may evaporate and the composition ratio may vary, and it takes too much time for production and it is difficult to industrialize.
- Compounding step is a step of mixing a metal oxide that is a raw material of the sputtering target.
- the raw material powders such as indium compound powder, gallium compound powder, and zinc compound powder are used.
- the specific surface area (BET specific surface area) of each metal compound as a target raw material can be measured by the method described in JIS Z 8830.
- the indium compound include indium oxide and indium hydroxide.
- the gallium compound include gallium oxide and gallium hydroxide.
- the zinc compound include zinc oxide and zinc hydroxide.
- an oxide is preferable because it is easy to sinter and it is difficult to leave a by-product.
- metallic zinc (zinc powder) is used as a part of the raw material. When zinc powder is used as a part of the raw material, the generation of white spots can be reduced.
- the purity of the raw material is usually 2N (99% by mass) or more, preferably 3N (99.9% by mass) or more, and particularly preferably 4N (99.99% by mass) or more. If the purity is lower than 2N, the durability of the resulting thin film may be reduced, or impurities may enter the liquid crystal side when used in a liquid crystal display, and baking may occur.
- a target such as a metal oxide
- an ordinary mixing and pulverizing machine such as a wet ball mill, a bead mill or an ultrasonic device.
- the calcination process is a process provided as needed, in which a mixture of compounds that are raw materials of the sputtering target is obtained and then the mixture is calcined.
- calcination it is easy to increase the density, which is preferable, but there is a risk of increasing the cost. Therefore, it is more preferable that the density can be increased without performing calcination.
- the metal oxide mixture is preferably heat-treated at 500 to 1200 ° C. for 1 to 100 hours. This is because the thermal decomposition of the indium compound, the zinc compound, and the tin compound may be insufficient under heat treatment conditions of less than 500 ° C. or less than 1 hour. On the other hand, when the heat treatment condition exceeds 1200 ° C. or exceeds 100 hours, coarsening of the particles may occur. Therefore, it is particularly preferable to perform heat treatment (calcination) in the temperature range of 800 to 1200 ° C. for 2 to 50 hours.
- the calcined product obtained here is pulverized before the following molding step and firing step.
- the molding step is a step of pressure-molding a mixture of metal oxides (or calcined product when the calcining step is provided) to form a compact. By this process, it is formed into a shape suitable as a target.
- the obtained calcined fine powder can be granulated and then molded into a desired shape by a molding process.
- Examples of the molding process that can be used in this step include press molding (uniaxial press), mold molding, cast molding, injection molding, and the like.
- press molding uniaxial press
- mold molding cast molding
- injection molding injection molding
- CIP cold isostatic pressure
- HIP hot isostatic pressure
- CIP cold isostatic pressure
- HIP hot isostatic pressure
- the surface pressure When using CIP (cold hydrostatic pressure or hydrostatic pressure press), it is preferable to hold the surface pressure at 800 to 4000 kgf / cm 2 for 0.5 to 60 minutes. More preferably, the surface pressure is maintained at 2000 to 3000 kgf / cm 2 for 2 to 30 minutes. Further, if the surface pressure is less than 800 kgf / cm 2 , the density after sintering may not increase or the resistance may increase. If the surface pressure exceeds 4000 kgf / cm 2 , the apparatus may become too large and uneconomical. If the holding time is less than 0.5 minutes, the density after sintering may not increase or the resistance may increase. If it exceeds 60 minutes, it may take too much time and be uneconomical.
- molding aids such as polyvinyl alcohol, methylcellulose, polywax, and oleic acid may be used.
- a sintering process is a process of baking the molded object obtained at the said formation process.
- the sintering is preferably performed in an oxygen gas atmosphere or under an oxygen gas pressure. If sintering is performed in an atmosphere that does not contain oxygen gas, the density of the target obtained cannot be sufficiently improved, and the occurrence of abnormal discharge during sputtering may not be sufficiently suppressed.
- the temperature is increased at a temperature increase rate in the predetermined atmosphere.
- the temperature rise may be stopped once during the temperature rise and held at the holding temperature, and sintering may be performed in two or more stages.
- the temperature lowering rate (cooling rate) of the atmosphere during firing is usually 4 ° C./min or less, preferably 2 ° C./min or less, more preferably 1 ° C./min or less, further preferably 0.8 ° C./min or less, Particularly preferred is 0.5 ° C./min or less.
- the desired crystal form of the present invention is easily obtained.
- cracks are unlikely to occur when the temperature drops.
- Reduction process is a process provided as needed which performs a reduction process in order to reduce the bulk resistance of the sintered compact obtained at the said sintering process as the whole target.
- Examples of the reduction method that can be applied in this step include a method using a reducing gas, vacuum firing, or reduction using an inert gas.
- 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.
- reduction treatment inert gas atmosphere such as argon or nitrogen, hydrogen atmosphere, or heat treatment in vacuum or low pressure.
- Processing step is to cut the sintered body obtained by sintering as described above into a shape suitable for mounting on a sputtering apparatus, and to mount a jig such as a backing plate. It is the process provided as needed for attaching.
- the sintered body is ground with, for example, a surface grinder so that the surface roughness Ra is 5 ⁇ m or less.
- the target material has a surface roughness Ra of 0.5 ⁇ m or less, and preferably has a ground surface with no directivity. If Ra is larger than 0.5 ⁇ m or the polished surface has directivity, abnormal discharge may occur or particles may be generated.
- the sputtering surface of the sputtering target may be further mirror-finished so that the average surface roughness Ra may be 1000 angstroms or less.
- polishing For this mirror finishing (polishing), a known polishing technique such as mechanical polishing, chemical polishing, and mechanochemical polishing (a combination of mechanical polishing and chemical polishing) can be used. For example, polishing to # 2000 or more with a fixed abrasive polisher (polishing liquid: water) or lapping with loose abrasive lapping (abrasive: SiC paste, etc.), and then lapping by changing the abrasive to diamond paste Can be obtained by:
- the surface is preferably finished with a 200 to 10,000 diamond grindstone, particularly preferably with a 400 to 5,000 diamond grindstone. If a diamond grindstone smaller than No. 200 or larger than 10,000 is used, the target may be easily broken. Such a polishing method is not particularly limited.
- the obtained sputtering target material is bonded to a backing plate.
- the thickness of the target material is usually 2 to 20 mm, preferably 3 to 12 mm, particularly preferably 4 to 6 mm. Further, a plurality of targets may be attached to one backing plate to make a substantially single target.
- ultrasonic cleaning can also be performed. This ultrasonic cleaning is effective by performing multiple oscillations at a frequency of 25 to 300 KHz. For example, ultrasonic cleaning is preferably performed by multiplying twelve types of frequencies in 25 KHz increments between frequencies of 25 to 300 KHz.
- the composition ratio (atomic ratio) of the prepared target can be obtained by analysis using an induction plasma emission analyzer (ICP-AES).
- Example 1 Production of target Two or more of the same oxide sintered bodies were produced simultaneously under the following conditions, and one was used for a destructive test (cut and evaluated).
- molding Press molding, surface pressure 400 kgf / cm 2 , 1 minute hold CIP (hydrostatic pressure press), surface pressure 2200 kgf / cm 2 , 5 minute hold
- Sintering Electric furnace Temperature rising rate 1 ° C./min Sintering temperature 1300 ° C Sintering time 20 hours Sintering atmosphere Oxygen atmosphere Cooling rate 0.3 ° C./min
- Post-treatment No heat treatment (reduction treatment) under reducing conditions was performed.
- G) Processing A sintered body having a thickness of 6 mm was ground and polished to a thickness of 5 mm.
- the upper and lower surfaces and sides were cut with a diamond cutter, and the surface was ground with a surface grinder to obtain a target material having a surface roughness Ra of 5 ⁇ m or less.
- One of the obtained sintered bodies for a target was cut at a site having a thickness of 2.5 mm for deep measurement.
- the surface of the obtained sintered body for target was blown with air and further subjected to ultrasonic cleaning for 3 minutes, and then bonded to a backing plate made of oxygen-free copper with indium solder to obtain a target.
- the surface roughness Ra of the target was 0.5 ⁇ m or less and had a ground surface with no directionality.
- the crystal form of the compound contained in the oxide sintered body was determined by comparing with the JCPDS card shown in Table 3.
- C Particle size ( ⁇ m) The particle diameter of the oxide crystal was measured with an electron probe microanalyzer (EPMA) and is shown in Table 1 as an average particle diameter.
- D Composition ratio (atomic ratio) A sample was taken from the target and analyzed with an induction plasma emission analyzer (ICP-AES) to determine the atomic ratio.
- ICP-AES induction plasma emission analyzer
- the identity of the crystal type is determined to be “identical” when there is no crystal type included in only one of the crystal types identified by XRD (all identified crystal types match), and included in only one of them.
- the case where there was a crystal form that was not determined was determined to be “not identical” (if the above was satisfied, a difference in peak intensity (about ⁇ 50%) was also determined to be the same).
- the identity of the element composition ratio (atomic ratio) on the surface of the sintered body for the target and the inside was determined to be the same within ⁇ 0.01 for each metal element. It was judged that the same in both the target sintered body surface and the internal particle size were within 5 ⁇ m.
- the identity of the specific resistance on the surface of the target sintered body and inside was judged to be the same within ⁇ 50%.
- the identity of the elemental composition ratio was judged by taking samples from the surface and the inside (the surface after cutting) and analyzing by ICP analysis to compare the composition ratio (atomic ratio).
- the substrate 10 was a glass substrate (Corning 1737). First, 10 nm thick Mo, 80 nm thick Al, and 10 nm thick Mo were laminated in this order on the substrate 10 by electron beam evaporation. A gate electrode 20 was formed on the laminated film by using a photolithography method and a lift-off method.
- a 200 nm thick SiO 2 film was formed on the gate electrode 20 and the substrate 10 by the TEOS-CVD method to form the gate insulating layer 30.
- the gate insulating layer may be formed by sputtering, but is preferably formed by CVD such as TEOS (tetraethoxysilane) -CVD or plasma enhanced chemical vapor deposition (PECVD). In the sputtering method, off current may be increased.
- a semiconductor film 40 (channel layer) having a thickness of 50 nm was formed by RF sputtering using the target prepared in (1) above. Then, it heat-processed for 60 minutes at 300 degreeC in air
- a SiO 2 film was deposited on the semiconductor film 40 as an etching stopper layer 60 (protective film) by sputtering.
- the protective film may be formed by a CVD method.
- the input RF power was 200 W.
- the substrate temperature was 50 ° C.
- the deposited oxide semiconductor film and protective film were processed into appropriate sizes by a photolithography method and an etching method.
- the etching stopper layer 60 After the formation of the etching stopper layer 60, Mo having a thickness of 5 nm, Al having a thickness of 50 nm, and Mo having a thickness of 5 nm were stacked in this order, and the source electrode 50 and the drain electrode 52 were formed by photolithography and dry etching. .
- Vth threshold voltage
- the film formation rate was determined by dividing the film thickness measured by a stylus type surface shape measuring device Decak (manufactured by ULVAC, Inc.) by the film formation time.
- TFT Stability (variation) of TFT characteristics
- a TFT was fabricated before and after 1000 hours of continuous discharge (film formation), and the variation in TFT characteristics (on-current) was evaluated.
- a sample having a variation of less than 10% was evaluated as A
- a sample having a variation of 10% or more and less than 20% was evaluated as B
- a sample having a variation of 20% or more was evaluated as C.
- Examples 2 to 9 and Comparative Examples 1 to 8 An oxide sintered body, a sputtering target, and a TFT were prepared and evaluated in the same manner as in Example 1 except that the compositions and conditions shown in Table 2-1 and Table 2-2 were used. The results are shown in Table 2-1 and Table 2-2.
- the Sn compounds used in Example 3 and Reference Examples 1 to 3, 5 and 6 described later are as follows. SnO 2 purity 4N, manufactured by High Purity Chemical Co., Ltd.
- Examples 10 and 11 When the semiconductor film was formed with a thickness of 50 nm, it was normally on, so a TFT was manufactured with the semiconductor film as 15 nm.
- An oxide sintered body, a sputtering target, and a TFT were prepared and evaluated in the same manner as in Example 1 except that the thickness of the semiconductor film was 15 nm and the composition and conditions shown in Table 2-1 were used. The results are shown in Table 2-1.
- Table 2-3 shows reference examples of sintered bodies not containing Ga. It can be seen that the sintered body containing no Ga hardly changes in the crystal type in the thickness direction of the target. From this result, the long-term stability problem of the present invention is a prominent problem in the case of a sintered body containing Ga (in the case of a sputtering target containing indium oxide, gallium oxide and zinc oxide as raw materials). Can be confirmed.
- Table 1 shows the elemental composition ratio (atomic ratio), particle size, and specific resistance of the target sintered bodies produced in Example 1 and Comparative Example 1.
- Tables 2-1 to 2-3 show various characteristics and the like of target sintered bodies and TFTs prepared in Examples, Comparative Examples, and Reference Examples.
- “ ⁇ ” in the crystal form of the target means a trace component (impurity component, main peak height is 50% or less of main component main peak height).
- Crystal type and JCPDS card No. Table 3 shows the comparison.
- the present invention it is possible to provide a sputtering target that is excellent in stability of characteristics of a thin film obtained when film formation is performed over a long period of time. According to the present invention, a thin film transistor having stable TFT characteristics can be efficiently provided.
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Abstract
Description
また、本発明を用いるとターゲットと薄膜の組成の差も小さくなり、薄膜のGaの含有比率がターゲットのGaの含有比率より極端に小さくなるという問題も改善することも見出した。
1.In、Zn、及びGaを含み、
表面と内部の化合物の結晶型が実質的に同一である酸化物焼結体からなるスパッタリングターゲット。
2.前記酸化物焼結体の表面の比抵抗(R1)と表面からt/2mm(tはスパッタリングターゲットの平均厚さである。)の深部の比抵抗(R2)の比R1/R2が、0.4以上2.5以下である、上記1に記載のスパッタリングターゲット。
3.前記酸化物焼結体のIn、Zn、及びGaの組成比(原子比)が、下記領域1~6のいずれかを満たす、上記1又は2に記載のスパッタリングターゲット。
領域1
Ga/(In+Ga+Zn)≦0.50
0.58≦In/(In+Zn)≦0.85
In/(In+Ga)≦0.58
領域2
Ga/(In+Ga+Zn)≦0.50
0.20≦In/(In+Zn)<0.58
In/(In+Ga)≦0.58
領域3
0.20<Ga/(In+Ga+Zn)
0.51≦In/(In+Zn)≦0.85
0.58<In/(In+Ga)
領域4
0.00<Ga/(In+Ga+Zn)<0.15
0.20≦In/(In+Zn)<0.51
0.58<In/(In+Ga)
領域5
0.00<Ga/(In+Ga+Zn)≦0.20
0.51≦In/(In+Zn)≦0.85
領域6
0.15≦Ga/(In+Ga+Zn)
In/(In+Zn)<0.51
0.58<In/(In+Ga)
4.前記実質同一の結晶型が、一種類の結晶型のみからなる、上記3に記載のスパッタリングターゲット。
5.前記一種類の結晶型が、In2Ga2ZnO7で表されるホモロガス結晶構造であり、かつ前記領域1の組成比を満たす、上記4に記載のスパッタリングターゲット。
6.前記一種類の結晶型が、InGaO3(ZnO)で表されるホモロガス結晶構造であり、かつ前記領域2又は領域3の組成比を満たす、上記4に記載のスパッタリングターゲット。
7.前記一種類の結晶型が、2θ=7.0°~8.4°、30.6°~32.0°、33.8°~35.8°、53.5°~56.5°及び56.5°~59.5°にCukα線のX線回折ピークを有する結晶構造であり、かつ前記領域4の組成比を満たす、上記4に記載のスパッタリングターゲット。
8.前記実質同一の結晶型が、ZnGa2O4で表されるスピネル結晶構造と、In2O3で表されるビックスバイト結晶構造とを含み、かつ前記領域1又は領域3の組成比を満たす、上記3に記載のスパッタリングターゲット。
9.前記実質同一の結晶型が、2θ=7.0°~8.4°、30.6°~32.0°、33.8°~35.8°、53.5°~56.5°及び56.5°~59.5°にCukα線のX線回折ピークを有する結晶構造と、In2O3で表されるビックスバイト結晶構造とを含み、かつ前記領域5の組成比を満たす、上記3に記載のスパッタリングターゲット。
10.前記実質同一の結晶型が、2θ=7.0°~8.4°、30.6°~32.0°、33.8°~35.8°、53.5°~56.5°及び56.5°~59.5°にCukα線のX線回折ピークを有する結晶構造と、InGaO3(ZnO)で表されるホモロガス結晶構造とを含み、かつ上記領域6の組成比を満たす、上記3に記載のスパッタリングターゲット。
11.下記(a)~(e)の工程を含む上記4、5、6及び8のいずれか1項に記載のスパッタリングターゲットの製造方法。
(a)原料化合物粉末を混合して混合物を調製する工程、
(b)前記混合物を成形して厚み6.0mm以上の成形体を調製する工程、
(c)雰囲気を昇温速度3℃/分以下で昇温する工程、
(d)前記昇温した成形体をさらに1280℃以上1520℃以下で2時間以上96時間以下焼結し、厚み5.5mm以上の焼結体を得る工程、
(e)前記焼結体の表面を0.25mm以上研削する工程
12.下記(a)~(e)の工程を含む上記5に記載のスパッタリングターゲットの製造方法。
(a)原料化合物粉末を混合して混合物を調製する工程、
(b)前記混合物を成形して厚み6.0mm以上の成形体を調製する工程、
(c)雰囲気を昇温速度3℃/分以下で昇温する工程、
(d)前記昇温した成形体をさらに1350℃超1540℃以下で2時間以上36時間以下焼結し、厚み5.5mm以上の焼結体を得る工程、
(e)前記焼結体の表面を0.25mm以上研削する工程
13.下記(f)~(i)の工程を含む上記8のスパッタリングターゲットの製造方法。
(f)原料化合物粉末を混合して混合物を調製する工程、
(g)前記混合物を成形して成形体を調製する工程、
(h)雰囲気を昇温速度10℃/分以下で昇温する工程、
(i)前記昇温した成形体をさらに1100℃以上1350℃以下で4時間以上96時間以下焼結する工程
本発明によれば、長期に渡る成膜を行った場合であっても、安定した薄膜トランジスタ特性が得られる。
ここで、「実質的に」とは、表面と内部を切断した面をX線回折測定(XRD)で測定した際、同定された結晶型の種類が同一であればよいことを意味する。
装置:(株)マルトー Million-Cutter 2 MC-503N
条件:ダイヤモンドブレード φ200mm
手順:
1.吸収版(アルミナ板)を温め、上面にアドフィックス(マルトー社製接着剤)を塗る。
2.ターゲットを置いた後、水で急冷することでターゲットを固定する。
3.吸収版を装置にセットし、ターゲットを切断する。
4.後は任意の切削面になるように1~3を繰り返す。
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
最大ピークの高さの比の差異が小さいほど、長期に渡って使用した際に、得られる薄膜の特性の変動が少なくなることが期待できる。
Ga/(In+Ga+Zn)≦0.50
0.58≦In/(In+Zn)≦0.85
In/(In+Ga)≦0.58
領域2
Ga/(In+Ga+Zn)≦0.50
0.20≦In/(In+Zn)<0.58
In/(In+Ga)≦0.58
領域3
0.20<Ga/(In+Ga+Zn)
0.51≦In/(In+Zn)≦0.85
0.58<In/(In+Ga)
領域4
0.00<Ga/(In+Ga+Zn)<0.15
0.20≦In/(In+Zn)<0.51
0.58<In/(In+Ga)
領域5
0.00<Ga/(In+Ga+Zn)≦0.20
0.51≦In/(In+Zn)≦0.85
領域6
0.15≦Ga/(In+Ga+Zn)
In/(In+Zn)<0.51
0.58<In/(In+Ga)
領域1
Ga/(In+Ga+Zn)≦0.45
0.58≦In/(In+Zn)≦0.80
In/(In+Ga)≦0.56
領域2
Ga/(In+Ga+Zn)≦0.40
0.35≦In/(In+Zn)<0.58
In/(In+Ga)≦0.58
領域3
0.20<Ga/(In+Ga+Zn)
0.60≦In/(In+Zn)≦0.85
0.60<In/(In+Ga)
領域4
0.09<Ga/(In+Ga+Zn)<0.15
0.35≦In/(In+Zn)<0.48
0.58<In/(In+Ga)
領域5
0.09<Ga/(In+Ga+Zn)≦0.20
0.53≦In/(In+Zn)≦0.75
領域6
0.17≦Ga/(In+Ga+Zn)
0.35≦In/(In+Zn)<0.48
0.60<In/(In+Ga)
領域6のさらに好ましい範囲は、下記の通りである。
領域6
0.18<Ga/(In+Ga+Zn)
0.38<Zn/(In+Ga+Zn)≦0.50
0.35≦In/(In+Zn)<0.48
0.60<In/(In+Ga)
領域1:光電流が小さいTFTの作製が可能
耐混酸耐性が高いTFTの作製が可能
実質的に単一の結晶型(In2Ga2ZnO7)からなるターゲッの作製が可能
領域1では、焼結温度等の作製条件を調整する、あるいはSn等の微量のドーパントを含有させることで、In2Ga2ZnO7の結晶型を生成させることができる。また、XRDでIn2Ga2ZnO7の結晶型以外の結晶型が確認されない酸化物焼結体を生成させることができる。In2Ga2ZnO7の結晶型を有することで、層状構造により導電性を高めることができる。
領域1では、焼結温度等の作製条件を調整することでIn2O3及びZnGa2O4の結晶型を含ませることができる。In2O3及びZnGa2O4の結晶型を有することにより、還元雰囲気での熱処理を行わなくともIn2O3中に酸素欠損を生成させることが容易となり、比抵抗を下げることができる。また、この結晶型を含むと研削量が少ない、あるいは研削を行わなくとも表面と中心部の結晶型を一致させることが容易である。これは、この結晶型が比較的低温で安定であるためと思われる。
実質的に単一の結晶型(InGaZnO4)からなるターゲットの作製が可能
TFTを作製した際、光電流が小さい
領域3では、焼結温度等の作製条件を調整することでIn2O3の結晶型を含ませることができる。In2O3の結晶型を有することにより、還元雰囲気での熱処理を行わなくともIn2O3中に酸素欠損を生成させることが容易となり、比抵抗を下げることができる。
領域3では、InとGaの比率が1:1でないにも係わらず、焼結温度等の作製条件を調整することで、In2Ga2ZnO7あるいはInGaZnO4で表されるホモロガス構造の結晶型を生成させることができる。ホモロガス構造の結晶型を有することで、層状構造により導電性を高めることができる。
実質的に単一の結晶型からなるターゲットの作製が可能
ターゲットの比抵抗が下げることが容易
領域4では、焼結温度等の作製条件を調整することで実質的に単一の結晶型からなるターゲットの作製が可能である。実質的に単一となることで、ターゲットの均一性が向上する。また、導電性が向上する。
ターゲットの比抵抗が下げることが容易
領域5では、2θ=7.0°~8.4°、30.6°~32.0°、33.8°~35.8°、53.5°~56.5°及び56.5°~59.5°にCukα線のX線回折ピークを有する結晶構造とIn2O3で表される結晶型を含むターゲットの作製が可能である。この結晶型の組合せにより、還元雰囲気での熱処理を行わなくともIn2O3中に酸素欠損を生成させることが容易となり、比抵抗を下げることができる。
また、領域5の組成を持つスパッタリングターゲットは、半導体層を薄膜化した高い移動度の薄膜トランジスタを得るのに適している。
(領域4よりも、光電流・混酸耐性・耐湿性が良好)
領域6では、2θ=7.0°~8.4°、30.6°~32.0°、33.8°~35.8°、53.5°~56.5°及び56.5°~59.5°にCukα線のX線回折ピークを有する結晶構造とInGaZnO4で表される結晶型を含むターゲットの作製が可能である。ホモロガス構造により導電性が向上する。
また、Ga/(In+Zn+Ga)が0.50以下で、小さいほど移動度やS値の向上が期待できる。
また、In/(In+Zn)が0.80以下で、小さいほどノーマリーオフに調整しやすくなることが期待できる。
成膜速度やキャリア密度の、酸素分圧の変化に対する感度の点では、領域3~領域6が好ましく、領域4及び領域5が特に好ましい。
In2Ga2ZnO7で表される結晶構造は、JCPDSカードNo.38-1097である。
0.005<Sn/(In+Ga+Zn+Sn)<0.10
上記Sn含有量の範囲は、下記がより好ましい。
0.01<Sn/(In+Ga+Zn+Sn)<0.05
InGaO3(ZnO)で表される結晶構造は、JCPDSカードNo.38-1104である。
X線回折測定(Cukα線)により得られるチャートにおいて、下記のA~Eの領域に回折ピークが観測される。
A.入射角(2θ)=7.0°~8.4°(好ましくは7.2°~8.2°)
B.2θ=30.6°~32.0°(好ましくは30.8°~31.8°)
C.2θ=33.8°~35.8°(好ましくは34.5°~35.3°)
D.2θ=53.5°~56.5°(好ましくは54.1°~56.1°)
E.2θ=56.5°~59.5°(好ましくは57.0°~59.0°)
条件2
2θが30.6°~32.0°(上記領域B)及び33.8°~35.8°(上記領域C)の位置に観測される回折ピークの一方がメインピークであり、他方がサブピークである。尚、ここでメインピークとは結晶型のXRDパターンの最大ピークの高さが最も高いものを指し、サブピークとは二番目の高さのものを指す。
In2O3で表されるビックスバイト結晶構造を含むことで、還元処理を行わなくとも比抵抗の低いターゲットを製造することが容易となる。
本発明の第一の製造方法は、下記(a)~(e)の工程を含むことを特徴とする。
(a)原料化合物粉末を混合して混合物を調製する工程、
(b)前記混合物を成形して厚み6.0mm以上の成形体を調製する工程、
(c)雰囲気を昇温速度3℃/分以下で昇温する工程、
(d)前記昇温した成形体をさらに1280℃以上1520℃以下で2時間以上96時間以下焼結し、厚み5.5mm以上の焼結体を得る工程、
(e)前記焼結体の表面を0.25mm以上研削する工程
昇温速度が3℃/分超であると、表面と深部の結晶型の種類が変動するおそれがある。これは、昇温時にターゲットの厚み方向に温度むら等が生じるためと思われる。
焼結時間は、通常2時間以上96時間以下であり、4時間以上48時間以下が好ましく、6時間以上24時間以下がより好ましい。
(a)原料化合物粉末を混合して混合物を調製する工程、
(b)前記混合物を成形して厚み6.0mm以上の成形体を調製する工程、
(c)雰囲気を昇温速度3℃/分以下で昇温する工程、
(d)前記昇温した成形体をさらに1350℃超1540℃以下で2時間以上36時間以下焼結し、厚み5.5mm以上の焼結体を得る工程、
(e)前記焼結体の表面を0.25mm以上研削する工程
(f)原料化合物粉末を混合して混合物を調製する工程、
(g)前記混合物を成形して成形体を調製する工程、
(h)雰囲気を昇温速度10℃/分以下で昇温する工程、
(i)前記昇温した成形体をさらに1100℃以上1350℃以下で4時間以上96時間以下焼結する工程
(1)配合工程
配合工程は、スパッタリングターゲットの原料である金属酸化物を混合する工程である。
仮焼工程は、スパッタリングターゲットの原料である化合物の混合物を得た後、この混合物を仮焼する、必要に応じて設けられる工程である。
仮焼を行うと、密度を上げることが容易になり好ましいが、コストアップになるおそれがある。そのため、仮焼を行わずに密度を上げられることがより好ましい。
従って、特に好ましいのは、800~1200℃の温度範囲で、2~50時間の条件で、熱処理(仮焼)することである。
成形工程は、金属酸化物の混合物(上記仮焼工程を設けた場合には仮焼物)を加圧成形して成形体とする工程である。この工程により、ターゲットとして好適な形状に成形する。仮焼工程を設けた場合には得られた仮焼物の微粉末を造粒した後、成形処理により所望の形状に成形することができる。
また、プレス成形(一軸プレス)後に、冷間静水圧(CIP)、熱間静水圧(HIP)等を行い2段階以上の成形工程を設けると再現性を高めるという点で好ましい。
焼結工程は、上記成形工程で得られた成形体を焼成する工程である。
還元工程は、上記焼結工程で得られた焼結体のバルク抵抗をターゲット全体として低減するために還元処理を行う、必要に応じて設けられる工程である。
還元性ガスによる還元処理の場合、水素、メタン、一酸化炭素や、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、アルゴンや、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。
加工工程は、上記のようにして焼結して得られた焼結体を、さらにスパッタリング装置への装着に適した形状に切削加工し、またバッキングプレート等の装着用治具を取り付けるための、必要に応じて設けられる工程である。
ここで、さらにスパッタリングターゲットのスパッタ面に鏡面加工を施して、平均表面粗さRaを1000オングストローム以下としてもよい。この鏡面加工(研磨)は機械的な研磨、化学研磨、メカノケミカル研磨(機械的な研磨と化学研磨の併用)等の、公知の研磨技術を用いることができる。例えば、固定砥粒ポリッシャー(ポリッシュ液:水)で#2000以上にポリッシングしたり、又は遊離砥粒ラップ(研磨材:SiCペースト等)にてラッピング後、研磨材をダイヤモンドペーストに換えてラッピングすることによって得ることができる。
このような研磨方法には特に制限はない。得られたスパッタリングターゲット素材をバッキングプレートへボンディングする。
尚、作製したターゲットの組成比(原子比)は、誘導プラズマ発光分析装置(ICP-AES)による分析で求めることができる。
(1)ターゲットの作製
下記条件で同時に同じ酸化物焼結体を2個以上作製し、1個を破壊試験用とした(切断し評価した)。
In2O3 純度4N、アジア物性材料(株)製
Ga2O3 純度4N、アジア物性材料(株)製
ZnO 純度4N、高純度化学(株)製
(b)混合:ボールミルで24時間混合した。
(c)造粒:自然乾燥
(d)成形:
プレス成形、面圧400kgf/cm2、1分保持
CIP(静水圧加圧装置)、面圧2200kgf/cm2、5分保持
(e)焼結:電気炉
昇温速度 1℃/分
焼結温度 1300℃
焼結時間 20時間
焼結雰囲気 酸素雰囲気
冷却速度 0.3℃/分
(f)後処理:還元条件下での熱処理(還元処理)は行わなかった。
(g)加工:厚さ6mmの焼結体を厚さ5mmに研削・研磨した。
尚、上下面・側辺をダイヤモンドカッターで切断して、表面を平面研削盤で研削して表面粗さRaが5μm以下のターゲット素材とした。
(h)得られたターゲット用焼結体のうち1個を、深部測定用に厚み2.5mmの部位で切断した。
(i)得られたターゲット用焼結体の表面をエアーブローし、さらに3分間超音波洗浄を行なった後、インジウム半田にて無酸素銅製のバッキングプレートにボンディングしてターゲットとした。ターゲットの表面粗さRaは0.5μm以下であり、方向性のない研削面を備えていた。
得られたターゲット用焼結体の評価は下記の方法で行った。
抵抗率計(三菱化学(株)製、ロレスタ)を使用し四探針法(JIS R 1637)に基づき測定、10箇所の平均値を抵抗率値とした。得られたターゲット用焼結体表面の比抵抗(R1)及び内部の比抵抗(R2)から、比(R1/R2)を算出した。
ターゲット用焼結体及びその切断片を下記条件で直接測定し、結晶型を決定した。
・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
酸化物結晶の粒径は、電子プローブマイクロアナライザ(EPMA)で測定し、表1に平均粒径で示す。
(d)組成比(原子比)
ターゲットから試料を採取し、誘導プラズマ発光分析装置(ICP-AES)で分析して原子比を求めた。
また、ターゲット用焼結体表面及び内部の元素組成比(原子比)の同一性は、各金属元素について±0.01以内を同一と判断した。
ターゲット用焼結体表面及び内部の粒径の同一性は、ともに5μm以内である場合を同一と判断した。
ターゲット用焼結体表面及び内部の比抵抗の同一性は、±50%以内を同一と判断した。
元素組成比の同一性は、表面及び内部(切断後の表面)から試料を採取し、ICP分析法で分析して組成比(原子比)を比較し判断した。
完成したスパッタリングターゲットを用いて、図1のチャンネルストッパー型薄膜トランジスタ(逆スタガ型薄膜トランジスタ)を作製し、評価した。
薄膜トランジスタの評価は、以下のように実施した。
(a)移動度(電界効果移動度(μ))
半導体パラメーターアナライザー(ケースレー4200)を用い、室温、遮光環境下で測定した。
半導体パラメーターアナライザー(ケースレー4200)を用い、室温、遮光環境下で測定した。
(i)混酸耐性評価用簡易素子の作製
シャドーマスクを用い簡易素子を作製した。熱酸化膜(100nm)付シリコン基板に半導体層形成用のシャドーマスクを付け、上記(3)と同様の条件で半導体膜を成膜した。次にソース・ドレイン電極形成用のシャドーマスクを付け、金電極をスパッタリングで成膜しソース・ドレイン電極とし、チャンネル長(L)200μm、チャンネル幅(W)1000μmの混酸耐性評価用簡易素子(TFT)とした。
駆動を確認できた混酸耐性評価用簡易素子(TFT)を混酸(リン酸系水溶液、30℃)に10秒間浸けた後、ドライエアー及び150℃15分で乾燥させた後TFT特性を測定した。ゲート電(Vg)15V、ドレイン電圧(Vd)15Vで10-6A以上のドレイン電流(Id)が確認できたものをA、できなかったものをBとして2段階で評価した。
光照射下と遮光環境下の測定を比較し、閾値電圧(Vth)の変動が2V未満のものをA、2V以上のものをBとして2段階で評価した。
(a)成膜速度の安定性(変動)
1000時間連続放電(成膜)前後の成膜速度を比較した。
変動が5%未満のものをA、5%以上10%未満のものをB、10%以上のものをCと評価した。
1000時間連続放電(成膜)前後にTFTを作製し、TFT特性(オン電流)の変動を評価した。変動が10%未満のものをA、10%以上20%未満のものをB、20%以上のものをCと評価した。
電子プローブマイクロアナライザ(EPMA)による組成分布の測定で、表面、深部ともにインジウムリッチ部分は周囲よりも酸素含有量が少ないことが確認できた。
同様に作製した薄膜を用いてターゲットとの組成比の違いを評価した。組成比はICP分析法で分析して求めた。ターゲットと薄膜の組成比はほぼ同一(薄膜の各元素の組成比がターゲットの各元素の組成比の±2%以内)であった。
表2-1及び表2-2に示す組成及び条件とした以外は実施例1と同様にして酸化物焼結体、スパッタリングターゲット及びTFTを作製し、評価した。結果を表2-1及び表2-2に示す。
尚、実施例3及び後述する参考例1~3、5及び6で用いたSn化合物は下記の通りである。
SnO2 純度4N、高純度化学(株)製
尚、実施例8において、XRDから求めたIn2O3のビックスバイト構造の格子定数は、格子定数a=10.074であった。
半導体膜50nmで作製した場合には、ノーマリーオンとなったため、半導体膜を15nmとしてTFTを作製した。半導体膜の厚みを15nmとし、表2-1に示す組成及び条件とした以外は実施例1と同様にして酸化物焼結体、スパッタリングターゲット及びTFTを作製し、評価した。結果を表2-1に示す。
また、EPMAによる測定で、表面、深部ともに実施例3のInの含有量が多い組織は周囲よりも錫(Sn)含有量が多いことが確認できた。
表2-3に、Gaを含まない焼結体の参考例を示した。Gaを含まない焼結体は、ターゲットの厚み方向の結晶型の変動が起りにくいことがわかる。この結果から、本発明の長期に渡る安定性という課題は、Gaを含む焼結体の場合(酸化インジウム、酸化ガリウム及び酸化亜鉛を原料として含むスパッタリングターゲットの場合)に顕著となる課題であることが確認できる。
実施例、比較例及び参考例で作製したターゲット用焼結体及びTFTの各種特性等を表2-1~2-3に示す。尚、ターゲットの結晶型における「△」は、微量成分(不純物成分、メインピークの高さが主成分のメインピークの高さの50%以下)を意味する。
結晶型とJCPDSカードNo.の対比を表3に示す。
本発明によれば、安定したTFT特性を有する薄膜トランジスタを効率的に提供することができる。
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 (13)
- In、Zn、及びGaを含み、
表面と内部の化合物の結晶型が実質的に同一である酸化物焼結体からなるスパッタリングターゲット。 - 前記酸化物焼結体の表面の比抵抗(R1)と表面からt/2mm(tはスパッタリングターゲットの平均厚さである。)の深部の比抵抗(R2)の比R1/R2が、0.4以上2.5以下である、請求項1に記載のスパッタリングターゲット。
- 前記酸化物焼結体のIn、Zn、及びGaの組成比(原子比)が、下記領域1~6のいずれかを満たす、請求項1又は2に記載のスパッタリングターゲット。
領域1
Ga/(In+Ga+Zn)≦0.50
0.58≦In/(In+Zn)≦0.85
In/(In+Ga)≦0.58
領域2
Ga/(In+Ga+Zn)≦0.50
0.20≦In/(In+Zn)<0.58
In/(In+Ga)≦0.58
領域3
0.20<Ga/(In+Ga+Zn)
0.51≦In/(In+Zn)≦0.85
0.58<In/(In+Ga)
領域4
0.00<Ga/(In+Ga+Zn)<0.15
0.20≦In/(In+Zn)<0.51
0.58<In/(In+Ga)
領域5
0.00<Ga/(In+Ga+Zn)≦0.20
0.51≦In/(In+Zn)≦0.85
領域6
0.15≦Ga/(In+Ga+Zn)
In/(In+Zn)<0.51
0.58<In/(In+Ga) - 前記実質同一の結晶型が、一種類の結晶型のみからなる、請求項3に記載のスパッタリングターゲット。
- 前記一種類の結晶型が、In2Ga2ZnO7で表されるホモロガス結晶構造であり、かつ前記領域1の組成比を満たす、請求項4に記載のスパッタリングターゲット。
- 前記一種類の結晶型が、InGaO3(ZnO)で表されるホモロガス結晶構造であり、かつ前記領域2又は領域3の組成比を満たす、請求項4に記載のスパッタリングターゲット。
- 前記一種類の結晶型が、2θ=7.0°~8.4°、30.6°~32.0°、33.8°~35.8°、53.5°~56.5°及び56.5°~59.5°にCukα線のX線回折ピークを有する結晶構造であり、かつ前記領域4の組成比を満たす、請求項4に記載のスパッタリングターゲット。
- 前記実質同一の結晶型が、ZnGa2O4で表されるスピネル結晶構造と、In2O3で表されるビックスバイト結晶構造とを含み、かつ前記領域1又は領域3の組成比を満たす、請求項3に記載のスパッタリングターゲット。
- 前記実質同一の結晶型が、2θ=7.0°~8.4°、30.6°~32.0°、33.8°~35.8°、53.5°~56.5°及び56.5°~59.5°にCukα線のX線回折ピークを有する結晶構造と、In2O3で表されるビックスバイト結晶構造とを含み、かつ前記領域5の組成比を満たす、請求項3に記載のスパッタリングターゲット。
- 前記実質同一の結晶型が、2θ=7.0°~8.4°、30.6°~32.0°、33.8°~35.8°、53.5°~56.5°及び56.5°~59.5°にCukα線のX線回折ピークを有する結晶構造と、InGaO3(ZnO)で表されるホモロガス結晶構造とを含み、かつ上記領域6の組成比を満たす、請求項3に記載のスパッタリングターゲット。
- 下記(a)~(e)の工程を含む請求項4、5、6及び8のいずれか1項に記載のスパッタリングターゲットの製造方法。
(a)原料化合物粉末を混合して混合物を調製する工程、
(b)前記混合物を成形して厚み6.0mm以上の成形体を調製する工程、
(c)雰囲気を昇温速度3℃/分以下で昇温する工程、
(d)前記昇温した成形体をさらに1280℃以上1520℃以下で2時間以上96時間以下焼結し、厚み5.5mm以上の焼結体を得る工程、
(e)前記焼結体の表面を0.25mm以上研削する工程 - 下記(a)~(e)の工程を含む請求項5に記載のスパッタリングターゲットの製造方法。
(a)原料化合物粉末を混合して混合物を調製する工程、
(b)前記混合物を成形して厚み6.0mm以上の成形体を調製する工程、
(c)雰囲気を昇温速度3℃/分以下で昇温する工程、
(d)前記昇温した成形体をさらに1350℃超1540℃以下で2時間以上36時間以下焼結し、厚み5.5mm以上の焼結体を得る工程、
(e)前記焼結体の表面を0.25mm以上研削する工程 - 下記(f)~(i)の工程を含む請求項8のスパッタリングターゲットの製造方法。
(f)原料化合物粉末を混合して混合物を調製する工程、
(g)前記混合物を成形して成形体を調製する工程、
(h)雰囲気を昇温速度10℃/分以下で昇温する工程、
(i)前記昇温した成形体をさらに1100℃以上1350℃以下で4時間以上96時間以下焼結する工程
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Also Published As
Publication number | Publication date |
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CN102597302A (zh) | 2012-07-18 |
TWI498436B (zh) | 2015-09-01 |
JP2011106003A (ja) | 2011-06-02 |
TW201124551A (en) | 2011-07-16 |
US20120228133A1 (en) | 2012-09-13 |
KR102027127B1 (ko) | 2019-10-01 |
KR20170097231A (ko) | 2017-08-25 |
EP2503019A4 (en) | 2014-06-04 |
EP2503019A1 (en) | 2012-09-26 |
KR20120084767A (ko) | 2012-07-30 |
CN102597302B (zh) | 2015-02-25 |
JP5591523B2 (ja) | 2014-09-17 |
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