CN103608924A - Oxide-type semiconductor material and sputtering target - Google Patents
Oxide-type semiconductor material and sputtering target Download PDFInfo
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- CN103608924A CN103608924A CN201280018536.5A CN201280018536A CN103608924A CN 103608924 A CN103608924 A CN 103608924A CN 201280018536 A CN201280018536 A CN 201280018536A CN 103608924 A CN103608924 A CN 103608924A
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- 239000004065 semiconductor Substances 0.000 title claims abstract description 49
- 239000000463 material Substances 0.000 title abstract description 19
- 238000005477 sputtering target Methods 0.000 title description 2
- 229910052751 metal Inorganic materials 0.000 claims abstract description 12
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 11
- 229910052718 tin Inorganic materials 0.000 claims abstract description 10
- 239000010408 film Substances 0.000 claims description 45
- 229910045601 alloy Inorganic materials 0.000 claims description 12
- 239000000956 alloy Substances 0.000 claims description 12
- 239000010409 thin film Substances 0.000 claims description 8
- 230000015572 biosynthetic process Effects 0.000 claims description 7
- 229910000967 As alloy Inorganic materials 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 abstract description 24
- 229910052725 zinc Inorganic materials 0.000 abstract description 5
- 239000002019 doping agent Substances 0.000 abstract description 3
- 239000011701 zinc Substances 0.000 description 19
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- 229910007541 Zn O Inorganic materials 0.000 description 1
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Abstract
The purpose of the present invention is to provide an oxide-type semiconductor material (ZTO: a Zn-Sn-O-type oxide) comprising a Zn oxide and an Sn oxide, which can be used as an alternative material for IGZO, is equivalent or superior to IGZO, has a carrier mobility as high as about 10 cm2/Vs, and does not require any high-temperature heat treatment. The present invention is an oxide-type semiconductor material comprising a Zn oxide and an Sn oxide, which is characterized in that Zr is contained as a dopant and the oxide-type semiconductor material has such a Zr content that the ratio of the number of atoms of the dopant relative to the total number of atoms of metal elements, i.e., Zn, Sn and Zr, is 0.005 or less.
Description
Technical field
The present invention relates to a kind of semi-conducting material that is provided with forming the semiconductor subassembly that forms the display unit such as liquid crystal display (display), especially also relate to and a kind ofly contain zinc (Zn) oxide and tin (Sn) oxide, and contain the oxide type semi-conducting material that zirconium (Zr) is usingd as alloy (dopant).
Background technology
In recent years, by the display unit of the slim TV of liquid crystal display representative etc., the increase of output, very remarkable with the tendency of large screen.And, with regard to this display unit, use thin-film transistor (Thin Film Transistor is called for short TFT) widely universal as the liquid crystal display of the active digit group type (active matrix type) of switch (switching) assembly.
Using as described in the display unit of TFT as switch module in, be to use oxide type semi-conducting material as the constituent material of TFT.With regard to this oxide type semi-conducting material, there is a kind of IGZO (In-Ga-Zn-O is oxide) that belongs to one of transparent oxide semiconductor material attracted attention (with reference to patent documentation 1).Because carrier (carrier) mobility of this IGZO is only second to the polysilicon using at present, and as amorphous silicon (amorphous silicon, therefore a-Si) property difference of TFT characteristic is little, can be used as material likely in semi-conducting material from now on and gradually starts extensively to be utilized.
Yet, in the liquid crystal display such as slim TV, there is the change of display mode.Specifically except plane shows (2D), more disclose can stereo display (3D) liquid crystal display.In the liquid crystal display of this stereo display (3D) type, be to be achieved in the mode by utilizing the control of switchable liquid crystal to make the left and right of display frame present different image.Therefore, for as described in the liquid crystal display of stereo display type, expectation can realize the switch module of response speed more at a high speed.
For corresponding to as described in the change of display mode of liquid crystal display, carried out all as the exploitation of the oxide type semi-conducting material of IGZO and so on.Become the TFT of the response speed of this high speed, high carrier transport factor is important.For example, in IGZO, than the carrier transport factor of a-Si IGZO, be to be greater than 1 to 2 figure place, for 5 to 10cm
2/ Vs left and right.Therefore, if this IGZO is for being used as the constituent material of the TFT of the switch module that belongs to stereo display type liquid crystal display, therefore in order to realize the more liquid crystal display of high standard, eagerly look forward to realizing the constituent material of TFT of the response speed of further high speed.
In addition, this IGZO is because must carry out more than 350 ℃ annealing (anneal) processing when forming TFT, therefore there is people to point out to be difficult to be used in as utilized the problem points that cannot carry out the display unit of high-temperature heat treatment of the organic EL panel of pliability (flexible) substrate etc. and electronic paper and so on.
And, from resource problem and the impact on human body and/or environment, eagerly look forward to not using the oxide type semi-conducting material of In and/or Ga, from this viewpoint, also must research and develop the replacement material of IGZO.
With regard to the replacement material of this IGZO, for example someone proposes the oxide type semi-conducting material (ZTO:Zn-Sn-O is oxide) (patent documentation 2, patent documentation 3, patent documentation 4, patent documentation 5) consisting of Zn oxide and Sn oxide.The ZTO system research and development of these background technologies are in order to realize high carrier transport factor.In these background technologies, though learn and can realize high carrier transport factor, the heat treatment temperature there is no when forming TFT examines fully, do not learn the applicable possibility to organic EL panel and/or electronic paper.
Especially, in patent documentation 5, though propose, in the oxide type semi-conducting material that contains Zn and Sn, to make to contain the most elements that comprise Zr as alloy, thereby form, make electronics carrier density for being greater than 1 * 10
15/ cm
3be less than 1 * 10
18/ cm
3oxide type semi-conducting material.But for this patent documentation 5, though for film (Sheet) resistance, examine the amount of alloy when heat treatment temperature when self-criticism does not form TFT fully and/or heat treatment etc.In this patent documentation 5, film resistor and carrier density have the relation of following formula.
Rs＝ρ／t
ρ＝1／(e.N.μ)
(Rs: thin-film electro resistance, ρ: than resistance value (specific insulation), N: carrier density, μ: carrier transport factor, t: thickness)
In other words, as described in patent documentation 5, when only learning film resistor value, and cannot determine thickness or carrier transport factor time, cannot determine carrier density.As can be seen here, present situation is the ZTO about the replacement material as IGZO, also cranes one and expects further to improve.
(background technology document)
(patent documentation)
Patent documentation 1: No. 4164562 specifications of Japan Patent.
Patent documentation 2: TOHKEMY 2009-123957 communique.
Patent documentation 3: TOHKEMY 2010-37161 communique.
Patent documentation 4: TOHKEMY 2010-248547 communique.
Patent documentation 5: TOHKEMY 2009-123957 communique.
Summary of the invention
(problem that invention institute wish solves)
The present invention is by being developed in view of described situation, object is for disclosing a kind of Zn of containing oxide and Sn oxide and as the oxide type semi-conducting material (ZTO:Zn-Sn-O is oxide) of the Zr of alloy, the replacement material of usining as IGZO, the carrier transport factor of this oxide type semi-conducting material be equal with IGZO more than, be 10cm
2the high carrier transport factor of/Vs left and right, and must 300 ℃ of above high-temperature heat treatment.
(solving the means of problem)
In order to solve described problem, the inventor etc., for the oxide type semi-conducting material being formed by Zn oxide and Sn oxide, make to contain situation that Zr usings as alloy through further investigation, discovery is in the alloy amount of set scope, have under high carrier transport factor state in keeping, needn't high-temperature heat treatment can realize can drive TFT ZTO film.
The present invention is the oxide type semi-conducting material that contains Zn oxide and Sn oxide, this oxide type semi-conducting material is to contain Zr as alloy, Zr amount is, with respect to the atomic ratio of the alloy of each atomicity summation of the Zn as metallic element, Sn, Zr, is below 0.005.
According to oxide type semi-conducting material of the present invention, can make carrier transport factor be equal with IGZO more than, and can realize 10cm
2the carrier transport factor of about/Vs, and by 250 ℃ of following heat treatments, forms the switch module of TFT etc.In addition, because not containing In, Ga, thus the also problem of No Assets, and reduce the impact on human body and/or environment.
At the Zr of the alloy of oxide type semi-conducting material of the present invention, be that the atomic ratio with respect to the alloy of each atomicity summation of the Zn as metallic element, Sn, Zr is made as below 0.005.Particularly, the atomicity that be order is x, Sn as the atomicity of the Zn of metallic element is that under the atomicity of y, the Zr situation that is z, with z/, (mode of x+y+z)≤0.005 contains alloy.If this atomic ratio surpasses 0.005, when the heat treatment of carrying out 300 ℃, carrier density becomes less than 1 * 10
15cm
-3, and cannot maintain good characteristic of semiconductor.If atomic ratio is below 0.005, because carrier density becomes less than 1 * 10
18cm
-3therefore, can realize with 350 ℃ of heat treatments after the equal following carrier density of IGZO film.The lower limit of alloy amount, As can realize the carrier density equal following with IGZO, if can form the switch module of TFT etc. by 250 ℃ of following heat treatments, is not limited to this numerical value.Under the inventor's etc. research, even if confirm that the Zr amount of alloy is 0.000085 (8.5 * 10 at atomic ratio
-5), also can adopt as oxide type semi-conducting material of the present invention.
The Zn of oxide type semi-conducting material of the present invention and Sn are A in the atomicity that makes the metallic element of Zn, while making the atomicity of the metallic element of Sn be B, be preferably the ratio to 0.8 with A/ (A+B)=0.4 and contain, and are more preferred from 0.6 to 0.7 ratio.If this A/ (A+B) is less than 0.4, the ratio of Sn can uprise, therefore the film that forms time institute's film forming in etch component when carrying out patterning, utilizes oxalic acid, is that the etching speed of etching solution can be slack-off terrifically, is unsuitable for production stage.In addition, if surpass 0.8, the ratio because of Zn uprises, therefore can make oxide type semi-conducting material for the patience step-down of water, and in the patterning step of the distribution using in generality when the formation of TFT assembly and/or semiconductor layer, because remover and/or the clean impact of pure water of resist itself is damaged ZTO film, and TFT component characteristic originally cannot be realized, and difference optionally, ZTO film can dissolve from substrate, come off, and cannot form TFT assembly.
Oxide type semi-conducting material of the present invention, effective in the extreme to the thin-film transistor of bottom gate polar form or top grid type.As described in, according to oxide type semi-conducting material of the present invention, because realizing the equal above carrier transport factor with IGZO, and can use in the Low Temperature Heat Treatment below 250 ℃, therefore for being suitable for the liquid crystal display of stereo display type of requirement high response speed, also applicable when formation utilizes the switch module of the organic EL panel of pliability substrate etc. and electronic paper etc.
While forming switch module by oxide semiconductor material of the present invention, utilizing by the formed film of this oxide semiconductor material is that effectively it is good when in order to this film of film forming, using sputtering method.
And, when forming the film of oxide type semi-conducting material of this case invention by this sputtering method, use belongs to by Zn oxide and Sn oxide and is formed, and containing Zr, Zr amount is that the atomic ratio with respect to the alloy of each atomicity summation of the Zn as metallic element, Sn, Zr is that sputter target below 0.005 is good.And, Zn and Sn, be in the atomicity that makes the metallic element of Zn be A, while making the atomicity of the metallic element of Sn be B, so that the target that contain ratio of A/ (A+B)=0.4 to 0.8 is good.Now, when the film forming of sputter, can use DC power supply or high frequency electric source, pulsed D c-power supply.Especially when using target, by using pulsed D c-power supply, because suppressing to result from the knot grain of target material surface or the formation of surperficial resistive formation, and carry out stable film forming, therefore become, be suitable for volume production step.
Using oxide type semi-conducting material of the present invention to carry out assembly while forming, though can carry out film forming by described sputtering method, but outside this also one-tenth embrane method beyond the sputter such as applicable pulsed laser deposition method.In addition, the method or the ink-jet method that in the nano particle with coating semiconductor material, are scattered in the dispersion liquid of solvent form circuit, also can use oxide type semi-conducting material of the present invention to form assembly.
(effect of invention)
According to oxide type semi-conducting material of the present invention, can realize the carrier transport factor equal above with IGZO, and with 250 ℃ of following Low Temperature Heat Treatment, can form the switch module of TFT etc.In addition, because not containing In, Ga, therefore the also problem of No Assets also can lower the impact on human body and environment.
Accompanying drawing explanation
Fig. 1 is the assembly skeleton diagram of TFT.
Fig. 2 is the measurement curve (1,200 ℃ of embodiment) of TFT characteristic.
Fig. 3 is the measurement curve (1,220 ℃ of embodiment) of TFT characteristic.
Fig. 4 is the measurement curve (1,250 ℃ of embodiment) of TFT characteristic.
Fig. 5 is the measurement curve (1,300 ℃ of embodiment) of TFT characteristic.
Fig. 6 is the measurement curve (1,200 ℃ of comparative example) of TFT characteristic.
Fig. 7 is the measurement curve (2,200 ℃ of comparative examples) of TFT characteristic.
Embodiment
Below, for embodiments of the invention, be illustrated.First the making for the sputter target (sputtering target) of the oxide type semi-conducting material about the present embodiment is illustrated.
Target is made: measure respectively scale both quantitative in atmospheric environment, impose in ZnO powder in the calcining of 500 ℃, atmospheric environment, impose the SnO in the calcining of 1050 ℃
2powder and the not ZrO of calcining
2powder, drops into resin container (pot) and (4L) with ball mill (ball mill), mixes.At this ball mill, be rotated the mixing of fast 130rpm, 12 hours incorporation times.Then, by mixed powder, the sieve with 500 microns of meshes (μ m), wire diameter 315 μ m screens.The mixed powder of the grain that sieves that removal coarse grain is divided, is fills up to the carbon diel processed of ψ 100 millimeters (mm), by hot pressing (hot press), makes sintered body.Hot pressing condition is that Ar gas flow is made as to 3L/min, till pressurization is warming up to 1050 ℃ under 9.4MPa after, to keep under the 25Mpa that pressurizes 90 minutes, make it the cooling sintered body that takes out again of nature.According to described order, to carry out forming the formation of sintered body target of the film of each atomic ratio shown in table 1.
Then, for using film build method and the film assessment thereof of the sputter target of the sintered body of having made to be illustrated.(TOKKI company manufactures: SML-464) carry out film forming to use commercially available one chip sputtering unit.Sputter condition is to be set to reach vacuum degree 1 * 10
-5pa, is used Ar/O
2mist is as sputter gas, sputter air pressure is set in 0.4Pa, and partial pressure of oxygen is 0.01Pa, in glass substrate (the NEC glass limited company manufacture: OA-10) of room temperature (25 ℃), by the DC sputter of 150W, carry out the film forming of thickness approximately 100 nanometers (nm).
It is to use (the SII NanoTechnology limited company manufacture: Vista Pro) carry out of ICP (inductively coupled plasma) emission spectrophotometer that the film of this film forming forms.In table 1, record the measuring value by Zn, Sn, Zr, the value of the atomic ratio of the Zn/ calculating (Zn+Sn) and Zr/ (Zn+Sn+Zr).In addition, while being used in the assembly of thin-film transistor (TFT) etc., the composition of this oxide type semi-conducting material, that assembly is cut off, with transmission electron microscope (TEM) etc., observe this assembly section on one side, identify oxide type semiconductor material layer on one side, with EDX, analyze this part and can identify.
Then, by each test portion of film forming, in atmospheric environment, carry out 1 hour annealing in process in 200 ℃, 220 ℃, 250 ℃, 300 ℃, and carry out respectively Hall effect measurement, in the hope of ratio resistance value, carrier transport factor, the carrier density of each test portion.It is that (Nanometrics japan limited company manufactures: HL5500PC), use each test portion that cuts out 10mm * 10mm four directions to carry out by commercially available Hall effect measuring equipment that this Hall effect measures.In table 1, show ratio resistance value, the carrier transport factor of each test portion, the result of carrier density.In addition, the heat treatment after this film forming, during from film forming, the underlayer temperature of (during sputter) is different, fixes stable film apply thermal energy for one end after film forming.For example, at the underlayer temperature of patent documentation 5, be the heat when putting on film forming, the atom disperseing by sputter, when being attached to substrate, along with the rising of this underlayer temperature, makes the atom that is attached to substrate produce the phenomenon that moves to stable place.In other words, the control of underlayer temperature during film forming, the summation of the energy when with sputter and the thermal energy of underlayer temperature, carries out the configuration again of atom, determines the crystalline state of film and/or regiospecific etc., therefore different from the heat treatment after film forming in the application's case.
TFT assessment: described film is made as to channel layer, uses metal mask to make thin-film transistor (TFT).In Fig. 1, be sectional skeleton diagram (A) and the planar dimension skeleton diagram (B) that shows established TFT assembly.As shown in Fig. 1 (A), the formation of TFT is film forming Al alloy (thickness 2000 in glass substrate 10 first
) using as gate electrode 20.Sputter air pressure at this is with 0.4Pa, carries out the DC sputter of input electric power 1000W.Follow film forming SiNx (thickness 3000
) using as dielectric film 30.At this, be that (samco company manufactures: PD-2202L) carry out film forming, and in 350 ℃ of plasma CVDs that carry out input electric power 250W of underlayer temperature by plasma CVD apparatus.The flow of unstrpped gas is to be made as SiH
4: NH
3: N
2=100cc:10cc:200cc.ZTO-ZrO described in continuation film forming
2film (thickness 300
) using as channel layer 40.Sputter air pressure at this is the DC sputter that carries out input electric power 150W under 0.4Pa.If the W/L=22 of channel.Finally by ITO film forming source electrode 50 (thickness 2000
) and drain electrode 51 (thickness 2000
).Sputter air pressure at this is under 0.4Pa, carries out the DC sputter of input electric power 600W.Size of components for the TFT making according to described mode is to be shown in Fig. 1 (B).The numerical value unit of each width of this Fig. 1 (B) is mm.
For the TFT having made, be that (Agilent Technologies company manufactures: the reception and registration characteristic that Semiconductor Device Analyzer B1500A) measures TFT by semiconductor analyzing device.The drain voltage applying during measurement (Vds) is 1 to 5V, and the measurement amplitude of grid voltage (Vgs) is to establish-10 to 20V.It at Fig. 2 to Fig. 7, is the result that shows the reception and registration characteristic that measures TFT.Fig. 2 to Fig. 5 is the TFT characteristic while showing embodiment 1 (each heat treatment temperature), and Fig. 6 is the TFT characteristic while showing comparative example 1 (200 ℃ of heat treatments), and Fig. 7 is the TFT characteristic while showing comparative example 2 (heat treatment).In addition, in Fig. 2 to Fig. 6, longitudinal axis left side is the logarithmic axis of drain current: Ids (A) value, and longitudinal axis right side is that the decimal point of √ Ids value represents axle.
[table 1]
As shown in table 1, Zr amount is atomic ratio 0.000085 (8.5 * 10 if
-5) to 0.00312 (3.12 * 10
-3), learn that the carrier density at 200 ℃ of heat treatment caudacorias is to fall into 1 * 10
15cm
-3above less than 1 * 10
18cm
-3scope.In addition, for comparative example 2, be in 300 ℃ of heat treatment temperatures, the carrier density that makes film is less than 1 * 10
15cm
-3.
In addition, the situation of embodiment 1, in the TFT of each heat treatment temperature characteristic, is result as shown in Figures 2 to 5.In addition in table 2, be presented at, the result of each TFT characteristic value of Fig. 2 to Fig. 5.In addition, field effect mobility [mu], the value obtaining for measure the result of TFT characteristic by forming TFT assembly, the carrier transport factor of table 1, is by the value that the Hall effect measurement of the film of film forming obtains.In addition, S value refers to the subcritical amplitude of oscillation value (subthreshold swing value) for showing transistorized characteristic.
[table 2]
As shown in Fig. 2 to Fig. 5 and table 2, learn the situation of embodiment 1, in whole heat treatment temperatures, on/off ratio is 5 figure places, is shown as good TFT characteristic.But, as Fig. 2, in 200 ℃ of the heat treatment temperatures of embodiment 1, be gradient at the straight line of on/off slightly slow down and.In addition for embodiment 2 to 5, also learn as same TFT characteristic.To this, as shown in Figure 6, in the situation of undoped comparative example 1 (200 ℃), confirm to become on/off not and the assembly that do not end, do not bring into play its function as channel layer of switch module.Then, as shown in 7 figure, in the situation of comparative example 2 (200 ℃), a little less than learning the effect in the extreme of on/off, do not bring into play the function as channel layer.
(utilizability in industry)
Oxide type semi-conducting material of the present invention is as very effective in the constituent material of the TFT of the requirement of the switch module of stereo display type liquid crystal display response speed more at a high speed.In addition, oxide type semi-conducting material of the present invention is because being used in Low Temperature Heat Treatment, therefore be suitable for utilizing organic EL panel and the electronic paper of pliability substrate etc., and from resource problem and on the value the high industry of the viewpoint of the impact of human body and environment also tool.
Claims (3)
1. an oxide type semi-conducting material, for containing the oxide type semi-conducting material of Zn oxide and Sn oxide, is characterized by:
Contain Zr as alloy, Zr amount is, with respect to the atomic ratio of the alloy of each atomicity summation of the Zn as metallic element, Sn, Zr, is below 0.005.
2. a thin-film transistor, is the bottom gate polar form of the oxide type semi-conducting material formation described in right to use requires the 1st or the thin-film transistor of top grid type.
3. a sputter target, is to give film forming in order to the formed film of oxide type semi-conducting material by described in 1 of claim the, being characterized as of this sputter target:
By Zn oxide and Sn oxide, formed; And
Contain Zr, Zr amount is, with respect to the atomic ratio of the alloy of each atomicity summation of the Zn as metallic element, Sn, Zr, is below 0.005.
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| PCT/JP2012/059486 WO2012165047A1 (en) | 2011-05-27 | 2012-04-06 | Oxide-type semiconductor material and sputtering target |
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| KR (1) | KR101523333B1 (en) |
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| CN109071356A (en) * | 2016-04-13 | 2018-12-21 | 株式会社钢臂功科研 | Oxidate sintered body and sputtering target and their manufacturing method |
| CN111465713A (en) * | 2018-03-16 | 2020-07-28 | 株式会社钢臂功科研 | Sputtering target and sputtering target |
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| JP2010050165A (en) * | 2008-08-19 | 2010-03-04 | Sumitomo Chemical Co Ltd | Semiconductor device, method of manufacturing the same, transistor substrate, light emitting device, and display device |
| CN101714870A (en) * | 2008-10-01 | 2010-05-26 | 三星电子株式会社 | Inverter, method of operating the same and logic circuit comprising inverter |
| CN101911303A (en) * | 2007-12-25 | 2010-12-08 | 出光兴产株式会社 | Oxide semiconductor field effect transistor and method for manufacturing the same |
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| CN102245531B (en) * | 2008-12-12 | 2016-05-11 | 出光兴产株式会社 | Composite oxide sintered body and sputtering target comprising same |
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| CN101911303A (en) * | 2007-12-25 | 2010-12-08 | 出光兴产株式会社 | Oxide semiconductor field effect transistor and method for manufacturing the same |
| JP2010050165A (en) * | 2008-08-19 | 2010-03-04 | Sumitomo Chemical Co Ltd | Semiconductor device, method of manufacturing the same, transistor substrate, light emitting device, and display device |
| CN101714870A (en) * | 2008-10-01 | 2010-05-26 | 三星电子株式会社 | Inverter, method of operating the same and logic circuit comprising inverter |
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| CN109071356A (en) * | 2016-04-13 | 2018-12-21 | 株式会社钢臂功科研 | Oxidate sintered body and sputtering target and their manufacturing method |
| CN111465713A (en) * | 2018-03-16 | 2020-07-28 | 株式会社钢臂功科研 | Sputtering target and sputtering target |
| CN111465713B (en) * | 2018-03-16 | 2022-05-03 | 株式会社钢臂功科研 | Sputtering target and sputtering target |
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| KR101523333B1 (en) | 2015-05-27 |
| TWI579393B (en) | 2017-04-21 |
| KR20130136537A (en) | 2013-12-12 |
| TW201303049A (en) | 2013-01-16 |
| WO2012165047A1 (en) | 2012-12-06 |
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