CN105074046A - Niobium oxide sputtering target, production method therefor, and niobium oxide film - Google Patents

Niobium oxide sputtering target, production method therefor, and niobium oxide film Download PDF

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CN105074046A
CN105074046A CN201480010227.2A CN201480010227A CN105074046A CN 105074046 A CN105074046 A CN 105074046A CN 201480010227 A CN201480010227 A CN 201480010227A CN 105074046 A CN105074046 A CN 105074046A
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niobium oxides
niobium
sputtering target
oxides
sintered compact
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梅本启太
张守斌
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Mitsubishi Materials Corp
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    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
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Abstract

The present invention provides a niobium oxide sputtering target that enables direct current (DC) sputtering, and also provides a production method and an niobium oxide film. This niobium oxide sputtering target is characterized by being a niobium oxide sintered body and in that the specific resistance thereof is 0.001-0.05 [Omega]cm over the entire area of the sintered body in the thickness direction.

Description

Niobium oxides sputtering target, its manufacture method and niobium oxides film
Technical field
The present invention relates to a kind of by direct current (DC) sputter film forming carried out to the niobium oxides film with high refractive index time the niobium oxides film of niobium oxides sputtering target, its manufacture method and use niobium oxides sputtering target film forming that is suitable for.
The application advocates based on February 26th, 2013 No. 2013-035575, the patent application of Japanese publication and on February 10th, 2014 in the right of priority of No. 2014-23246, the patent application of Japanese publication, and its content is applied at this.
Background technology
In recent years, from the face such as to prevent of effective utilization of energy-conservation, resource or environmental pollution, the solar cell directly sunlight being converted to electric energy receives publicity and develops.At this, as photoelectric conversion material, there will be a known and do not use silicon, and use by the solar cell of the oxide semiconductor of organic pigment sensitization.In photoelectric conversion material oxide semiconductor, use the metal-oxide semiconductor (MOS) being adsorbed with spectral sensitization pigment, as this metal oxide, such as known use niobium oxides (such as referenced patent document 1 ~ 3).
On the other hand, as the optical application of niobium oxides film, except thin-film solar cells, also relate to from the heat-reflecting glass or antireflection film of individual layer, optionally reflect with the light of specific wavelength further or multiple field such as anti-reflection coating, refection-enhancing coating, interference filter, light polarizing film of assembly of thin films of patten's design of spectral response curve excellence of transmission.Further, also studying the film by clamping nesa coating or metal, conductive ceramic etc. in a part for multilayer film with the various function such as electroconductibility or heat reflection, being used as that there is multilayer film that the is antistatic or function such as heat reflection, cut-out hertzian wave.
When forming this niobium oxides film, in the manufacture of thin-film solar cells, flat-panel monitor etc., needing the situation of large-area substrates more, using spatter film forming method.And, in spatter film forming method, also especially utilize the most applicable large-area film forming of DC sputtering method of direct-current discharge.But, when carrying out film forming by the niobium oxides film of DC sputtering method to high refractive index, use the reactive sputtering sputtered under oxygen containing atmosphere by the metal niobium sputtering target with electroconductibility.But the film forming speed of the film obtained by the method is extremely slow, therefore exists and produces rate variance, the large problem in the manufacture of cost height and so on.
Therefore, proposition has commercially available highly purified Nb 2o 5powder is filled in the hot pressing mould of carbon, in argon gas atmosphere, keep 1 hour, and the sintered compact obtained by carrying out hot pressing manufactures niobium oxides sputtering target (such as referenced patent document 4) at the temperature of 1100 DEG C ~ 1400 DEG C of scopes.Although this niobium oxides sputtering target is made up of niobium oxides, because this niobium oxides is than stoichiometric composition oxygen defect a little, therefore its ratio resistance is 0.45 below Ω cm, carries out film forming by DC sputtering method.
And, the sputtering target be made up of niobium oxides sintered compact is when making by hot pressing, the compression aspect of this hot pressing is only single shaft direction, and carry out in inert gas atmosphere, therefore to obtain large-area molding, the amount that then there is the rare gas element of filling increases, the shortcoming that manufacturing cost uprises, and the relative density due to niobium oxides sintered compact is low to about 90%, when using as sputtering target, exist and be difficult to obtain stable electric discharge, easy generation be full of cracks or damaged, cannot life-time service, and the problem that productivity declines.
As the example solving this problem, propose have more than 99.9 % by weight, relative density be more than 90% and average crystallite particle diameter be the sputtering target (such as referenced patent document 5) be made up of niobium oxides sintered compact that the niobium oxides of 5 ~ 20 μm carries out hot pressing.Further, as another example, propose to have and plasma spray coating is carried out to reduced form oxide compound and the oxide sputtering target (such as referenced patent document 6) that formed.These sputtering targets all have electroconductibility, and sheet resistance value is lower, and compared with therefore sputtering with general reactive DC, film forming speed is high, are applicable to DC sputtering.
Patent documentation 1: Japanese Unexamined Patent Publication 2000-113913 publication (A)
Patent documentation 2: Japanese Unexamined Patent Publication 2003-123853 publication (A)
Patent documentation 3: Japanese Unexamined Patent Publication 2010-271720 publication (A)
Patent documentation 4: Japanese Unexamined Patent Publication 2005-256175 publication (A)
Patent documentation 5: Japanese Unexamined Patent Publication 2002-338354 publication (A)
Patent documentation 6: Japanese Unexamined Patent Publication 2003-98340 publication (A)
But, in the niobium oxides sputtering target proposed in above-mentioned patent documentation 4, owing to using the niobium oxides (Nb of anaerobic defect 2o 5) raw material powder directly carries out hot pressing, therefore the surface portion of sintered compact is reduced and becomes the niobium oxides (Nb of oxygen damage condition 2o 5-X), but reduction reaction does not proceed to target inside, likely remains in target inside the niobium oxides (Nb be not reduced 2o 5).
Such as, when wanting manufacturing dimension to be diameter more than sputtering target more than 5mm of 100mm, thickness, although target surface portion is reduced, along with the inside entering target, remain the unreduced niobium oxides (Nb without electroconductibility 2o 5).If sputter with this sputtering target, then DC sputtering can be carried out in the reduction portion of surface portion.But, if along with sputtering carrying out, dig to target inside into, then because the portion of reduction without electroconductibility is exposed to surface, exist cause DC sputter stopping problem.
Further, in the sputtering target proposed in above-mentioned patent documentation 5, due to through raw material powder pre-burning operation, formally burn till, 3 stages of hip moulding (HIP) operation under reducing atmosphere and manufacturing, therefore lack production.And, due to after the sintered compact that the density sintered in acquisition uprises, carry out reduction treatment, therefore identical with the situation of above-mentioned patent documentation 4, likely remain the portion of reduction in target inside.
And, in the manufacture method of the reduced form oxide sputtering target proposed in above-mentioned patent documentation 6, owing to forming reduced form oxide compound by sputtering process, thus implement reduction treatment in advance, therefore the ratio resistance of target inside is lower, but by the sputtering target of sputtering process, generally can not get high-density and the target of high-quality.And, when manufacturing the sputtering target thick more than 5mm, owing to producing the inequality of stress etc. in a thickness direction, therefore there is the problem cannot carrying out stable DC sputtering.
Summary of the invention
Therefore, the object of the present invention is to provide a kind of thickness direction throughout sputtering target (depth of corrosion direction) by the niobium oxides (Nb of oxygen damage condition 2o 5-X) form, the ratio resistance that hits in the whole region of thickness direction is lower, and can carry out stable DC sputtering all the time, and can improve niobium oxides sputtering target and the manufacture method thereof of rate of film build.
The present inventor etc. are conceived in the niobium oxides sputtering target proposed in above-mentioned each patent documentation, the ratio resistance of its target is lower at target surface element, more more uprise this point to the inner ratio resistance of target, even if specify that as also reducing this ratio resistance in target inside and making it change uniform target, in advance reduction treatment is implemented to niobium oxide powder, generate the niobium oxides (Nb of oxygen damage condition 2o 5-x), and by it can be used as raw material powder to sinter, obtaining the ratio resistance that to hit in the whole region of thickness direction lower, and the niobium oxides sputtering target of stable DC sputtering can be carried out all the time.
Therefore, under reducing atmosphere to commercially available niobium oxide powder (Nb 2o 5powder) implement reduction treatment (such as carry out high temperature and burn till process in the crucible of carbon, or heat-treat in containing the reducing gas of hydrogen, carbon monoxide etc.), make the niobium oxide powder (Nb of oxygen damage condition 2o 5-xpowder), by obtained Nb 2o 5-xpowder, as raw material powder, sinters the sintering condition of this raw material powder according to regulation, obtains niobium oxides (Nb 2o 5-x) sintered compact.Its sintered compact is machined into regulation shape and makes the result of niobium oxides sputtering target, confirm the whole region at target thickness direction, target ratio resistance can be reduced, in the film forming of niobium oxides film using this niobium oxides sputtering target, stable DC sputtering can be carried out all the time.And, also specify that niobium oxide powder (Nb 2o 5powder) when carrying out reduction treatment, the niobium oxides (Nb that electroconductibility is high can be generated 12o 29).Further, following opinion is obtained: to containing this niobium oxides (Nb 12o 29) niobium oxide powder carry out sintering and in the sintered compact obtained, also discrete distribution has this Nb 12o 29phase, this phase have the further reduction helping target ratio resistance.
Therefore, the present invention is obtained by above-mentioned opinion, in order to solve described problem, adopts following formation.
(1) niobium oxides sputtering target of the present invention is niobium oxides sintered compact, and wherein, in the whole region of the thickness direction of described niobium oxides sintered compact, ratio resistance is 0.001 ~ 0.05 Ω cm.
(2) the niobium oxides sputtering target of described (1), wherein, the average crystallite particle diameter of the niobium oxides crystal grain in described niobium oxides sintered compact is less than 100 μm.
(3) the niobium oxides sputtering target of described (1) or (2), wherein, the maximum difference of the ratio resistance of the target thickness direction of described niobium oxides sintered compact is 0.02 below Ω cm, and the maximum difference of ratio resistance in sputter face is 0.02 below Ω cm.
(4) described niobium oxides sputtering target any one of (1) ~ (3), wherein, described niobium oxides sintered compact is by meeting chemical formula: Nb 2o 5-xthe niobium oxides of (wherein, x=0.005 ~ 0.1) is formed.
(5) described niobium oxides sputtering target any one of (1) ~ (4), wherein, described niobium oxides sintered compact meets chemical formula by use: Nb 2o 5-xthe niobium oxide powder of (wherein, x=0.005 ~ 0.1) carries out sintering and obtaining.
(6) the niobium oxides sputtering target any one of described (1) ~ (5), wherein, in the matrix of described niobium oxides sintered compact, is evenly distributed with Nb 12o 29phase.
(7) manufacture method of niobium oxides sputtering target of the present invention, has: reduction operation, carries out reduction treatment to obtain oxygen defect niobium oxide powder to niobium oxide powder; And sintering circuit, under nonoxidizing atmosphere, sinter obtained oxygen defect niobium oxide powder to obtain sintered compact.
(8) manufacture method of the niobium oxides sputtering target of described (7), wherein, in described reduction operation, heat-treats to niobium oxide powder with the temperature of more than 500 DEG C under reducing atmosphere, generates and meets chemical formula: Nb 2o 5-xthe niobium oxide powder of the oxygen damage condition of (wherein, x=0.005 ~ 0.1).
(9) manufacture method of the niobium oxides sputtering target of described (7) or (8), wherein, before described sintering circuit, has the mixed processes of the oxygen level deviation reducing described acquired oxygen defect niobium oxide powder.
(10) manufacture method of described niobium oxides sputtering target any one of (7) ~ (9), wherein, the crystallization particle diameter of described oxygen defect niobium oxide powder is less than 100 μm.
(11) niobium oxides film of the present invention, uses niobium oxides sputtering target spatter film forming described in any one of described (1) ~ (6).
In the present invention, niobium oxides sputtering target is made up of the sintered compact of the niobium oxides sintering oxygen damage condition.General niobium oxides (Nb 2o 5) do not show electroconductibility, if but reduction treatment is implemented to this niobium oxide powder, then generate the niobium oxides (Nb of oxygen damage condition 2o 5-x) powder, it shows electroconductibility.By adjusting this oxygen defect amount x, the ratio resistance of niobium oxide powder changes.Therefore, if by the niobium oxides (Nb of oxygen damage condition 2o 5-x) powder sinters as raw material, then obtained sintered compact shows lower ratio resistance in the whole region of the thickness direction of this sintered compact.When using the niobium oxides sputtering target of this sintered compact to carry out film forming to niobium oxides film, in order to carry out direct current (DC) sputtering, preferably its ratio resistance is 0.05 ~ 0.001 Ω cm.
In niobium oxides sputtering target of the present invention, the average crystallite particle diameter of the niobium oxides crystal grain in niobium oxides sintered compact is less than 100 μm.If this average crystallite particle diameter is comparatively large, then frequently there is paradoxical discharge when sputtering, stable DC sputtering cannot be carried out, therefore its average crystallite particle diameter is set to less than 100 μm.
In addition, the characteristic of the niobium oxides film formed to improve use niobium oxides sputtering target to carry out sputtering, in niobium oxides sputtering target of the present invention, can add Cr, Ce, Zr, Hf, Y, Mo, W, Si, Al, B etc. as target composition.
The manufacture method of niobium oxides sputtering target of the present invention, has reduction treatment niobium oxide powder and obtains the reduction operation of the niobium oxide powder of oxygen damage condition and obtain the sintering circuit of sintered compact by sintering in nonoxidizing atmosphere the niobium oxide powder of obtained oxygen damage condition.
In this reduction treatment operation, such as, by commercially available niobium oxide powder (Nb 2o 5powder) add in the crucible of carbon, at the reductive condition of regulation, namely in a vacuum or in rare gas element, carry out reduction treatment with the heating temperatures 3 ~ 5 hours of 500 ~ 1100 DEG C, make the niobium oxides (Nb of oxygen damage condition 2o 5-x) powder.In this reduction treatment, in order to carry out chemical formula: Nb 2o 5-xreduction treatment till (wherein, x=0.005 ~ 0.1), preferential oxidation niobium powder (Nb 2o 5powder) particle diameter be 2 ~ 25 μm.For obtained reduced powder, in order to reduce the oxygen level deviation of oxygen defect niobium oxide powder as required, in dry ball device, with the rotating speed of 80 ~ 120rpm mixing 1 ~ 3 hour.Then, by obtained Nb 2o 5-xthe sieve that powder is 32 ~ 600 μm by aperture carries out classification, becomes less than 100 μm to make median size.
Further, in sintering circuit afterwards, by the Nb obtained in reduction operation 2o 5-xthis raw material powder, as raw material powder, is filled in mould by powder, at the sintering condition of regulation, namely to being exhausted in vacuum tank until 10 -2after till the arrival vacuum pressure of Torr (1.3Pa), keep 2 ~ 3 hours at the temperature of 800 ~ 1300 DEG C, sinter under the pressure of 20 ~ 60MPa, make the niobium oxides (Nb of oxygen damage condition thus 2o 5-x) sintered compact.Further, this sintered compact is machined into regulation shape, makes niobium oxides sputtering target.
In addition, during sintering, what all can use under hot pressing (HP), hip moulding method (HIP method) or reducing atmosphere is normal pressure-sintered.
Niobium oxides film of the present invention uses the niobium oxides sputtering target spatter film forming of the invention described above.
As mentioned above, according to the present invention, because the sintered compact of niobium oxides sputtering target is by sintering the niobium oxides (Nb of oxygen damage condition 2o 5-x) and obtain, therefore in the whole region of the thickness direction (depth of corrosion direction) of target, by the niobium oxides (Nb of oxygen damage condition 2o 5-x) form, and, owing to being dispersed with the higher Nb of electroconductibility 12o 29phase, therefore, it is possible to reduce target ratio resistance in the whole region of thickness direction, and due in target ratio resistance even, therefore stable DC sputtering can not only be carried out all the time, and by reducing target ratio resistance, the rate of film build of sputtering can be improved, contribute to boosting productivity.
Accompanying drawing explanation
Fig. 1 be illustrate sputtering target sputter face in direction ratio resistance measure figure.
Fig. 2 is the concrete example to niobium oxides sputtering target involved in the present invention, is measured the Elemental redistribution image of each element of the tissue of sputtering target by EPMA.
Fig. 3 represents the concrete example to niobium oxides sputtering target involved in the present invention, the figure of the analytical results undertaken by X-ray diffraction (XRD).
Fig. 4 represents the concrete example to the niobium oxides sputtering target of conventional art, the figure of the analytical results undertaken by X-ray diffraction (XRD).
Embodiment
Next, to niobium oxides sputtering target of the present invention and manufacture method thereof, be specifically described by following examples.
[the 1st embodiment]
< reduction treatment >
At the niobium oxide powder (Nb that sintering is commercially available 2o 5powder) front, implement reduction treatment, make the niobium oxide powder (Nb of oxygen damage condition 2o 5-xpowder).
First, by commercially available niobium oxide powder (Nb 2o 5powder) add in the crucible of carbon, according to the reductive condition shown in table 1, in a vacuum, with the temperature of 500 ~ 1100 DEG C, heat 3 ~ 5 hours and carry out reduction treatment.Secondly, the niobium oxide powder (Nb of oxygen damage condition will be become by this reduction treatment 2o 5-xpowder) add in plastic bottle (polyethylene bottle) with zirconia ball, in dry ball device, with the rotating speed of 80 ~ 120rpm mixing 1 ~ 3 hour.Then, by obtained Nb 2o 5-xthe sieve that powder is 32 ~ 600 μm by aperture carries out classification, becomes less than 100 μm to make median size.
The manufacture > of < target
By the Nb so obtained 2o 5-xthis raw material powder, as raw material powder, is filled in mould by powder, according to the sintering method shown in table 2 and sintering condition, and will to being exhausted in vacuum tank until 10 -2after till the arrival vacuum pressure of Torr (1.3Pa), keep 2 ~ 3 hours at the temperature of 900 ~ 1200 DEG C, under the pressure of 15 ~ 50MPa, carry out hot pressing (HP), make niobium oxides (Nb thus 2o 5-x) sintered compact.Further, mechanical workout will be carried out to this sintered compact, make the niobium oxides sputtering target with the embodiment 1,4,7,9 of diameter 152.4mm.
Further, by obtained Nb 2o 5-xpowder, as raw material powder, keeps 2 ~ 3 hours, carries out hip moulding (HIP), obtain niobium oxides (Nb thus under the pressure of 35 ~ 60MPa at the temperature of 800 ~ 1200 DEG C 2o 5-x) sintered compact, and make the niobium oxides sputtering target of embodiment 2,3,5,8.And, by obtained Nb 2o 5-xpowder, as raw material powder, keeps 5 hours at the temperature of 1200 DEG C, normal pressure-sintered under reducing atmosphere, obtains niobium oxides (Nb thus 2o 5-x) sintered compact, and make the niobium oxides sputtering target of embodiment 6.
[comparative example]
In order to compare with the niobium oxides sputtering target of embodiment, prepare the niobium oxides sputtering target of comparative example 1 ~ 3.In comparative example 1 and 2, sinter commercially available niobium oxide powder (Nb 2o 5powder), manufacture niobium oxides sputtering target, in comparative example 1, sinter with hot pressing, in comparative example 2, sinter with hip moulding method.Further, in comparative example 3, by commercially available niobium oxide powder (Nb 2o 5powder) in the crucible of carbon, carry out reduction treatment with the heating temperatures 5 hours of 300 DEG C, by obtained niobium oxide powder (Nb 2o 5-xpowder) carry out hot pressing and make sintered compact.
[table 1]
[table 2]
The mensuration > of < oxygen defect amount
To embodiment 1 ~ 9 and comparative example 1 ~ 3, by the oxygen defect amount in the niobium oxide powder (reducing powder) after following step measurements reduction treatment.
(step 1) will carry out 1 hour with 100 DEG C heating to obtained reducing powder, and carry out drying.
The dried powder 1g of (step 2) weighing, adds heat treatment in advance to and in the crucible of constant weight.
The weight of dried powder is set to a, the weight of crucible is set to b.
(step 3), in electric furnace, carries out the heating of 2 hours with 800 DEG C, cool 30 ~ 60 minutes, weigh accurately in moisture eliminator.Repeat this step till reaching constant weight.The weight of the crucible after thermal treatment and powder is set to c.
(step 4), according to following calculation formula, calculates oxygen defect amount x.
X=[b/ (c-b) × (Nb nucleidic mass × 2+O nucleidic mass × 5)-Nb nucleidic mass × 2]/O nucleidic mass
Repeat more than 3 times step 1 ~ 4, the mean value of obtained oxygen defect amount x is set to oxygen defect amount.In addition, this oxygen defect amount x represents the total amount of the oxygen of the defect in the niobium oxide powder of reduction treatment, with chemical formula: Nb 2o 5-xrepresent oxygen defect niobium oxides.
Above result is shown in " reducing powder oxygen defect " hurdle of table 1.
In addition, to the niobium oxides sputtering target of embodiment 1 ~ 9 and comparative example 1 ~ 3, the flow measurement of oxygen defect is carried out.Measure by following step.
When measuring the oxygen defect of sputtering target, in agate mortar, pulverizing obtained sintered compact, the powder that the mode process identical with above-mentioned steps obtains, obtaining oxygen defect amount x by above-mentioned calculation formula.
Above result is shown in " sintered compact oxygen defect " hurdle of table 2.
Next, to niobium oxides reduced powder and the sputtering target of embodiment 1 ~ 9 and comparative example 1 ~ 3, Nb is carried out 12o 29the presence or absence evaluation of phase.
< is by the Nb of EPMA image 12o 29the observation > of phase
To an example of niobium oxides sputtering target involved in the present invention, the Elemental redistribution image obtained by EPMA (field emission electron probe-microanalyser) is shown in Fig. 2.The distribution situation of composition image (COMP image), Nb, O can be observed from the photo of 3 figure.
In addition, the Elemental redistribution image of EPMA is chromatic image originally, but in the photo of Fig. 2, converts black-and-white image display to, therefore in this photo, whiter, represents that the concentration of this element is higher.Specifically, about in the distribution image of Nb and O, observe white portion and be evenly distributed, and there is niobium oxides, but in the distribution image of COMP image, in the matrix of the niobium oxides of display grey, can Nb be observed 12o 29the situation of phase discrete distribution.
< is by the Nb of XRD 12o 29the presence or absence of phase evaluates >
XRD determining condition
The preparation of test portion: pulverize obtained sintered compact in agate mortar, is used as mensuration test portion.
Device: electric corporation of science system (RINT-Ultima/PC)
Pipe ball: Cu
Tube voltage: 40kV
Tube current: 40mA
Sweep limit (2 θ): 5 ° ~ 80 °
Slit sizes: disperse (DS) 2/3 degree, scattering (SS) 2/3 degree, light (RS) 0.05mm
Measure step pitch width: when 2 θ be 0.04 degree
Sweep velocity: per minute 4 degree
Test portion platform speed of rotation: 30rpm
In the peak value of the XRD figure type obtained by said determination, belong to from Nb when detecting 12o 29being set to " having " during the peak value of (400) face of phase, the peak value of (1400), being set to "None" when not detecting.
To an example of niobium oxides sputtering target involved in the present invention, the figure of XRD analysis result is shown in Fig. 3.According to this figure, can find out and detect and belong to from Nb 12o 29the peak value of (400) face of phase, the peak value of (1400).On the other hand, to an example of the niobium oxides sputtering target of conventional art (comparative example), the figure of XRD analysis result is shown in Fig. 4, but does not detect from Nb 12o 29the peak value of phase.
In addition, for Nb 12o 29the ownership of phase, with reference to Nb described in following paper 12o 29.[Norin，R.ActaChem.Scand.，Vol.17，P1391(1963)]
The evaluation result of the niobium oxides reduced powder of one embodiment 1 ~ 9 and comparative example 1 ~ 3, is shown in " the Nb of table 1 12o 29the presence or absence of phase " in hurdle, and about the evaluation result of sputtering target, be shown in " the Nb of table 2 12o 29the presence or absence of phase (XRD) " in hurdle.
The mensuration > of < ratio resistance
To the niobium oxides sputtering target of obtained embodiment 1 ~ 9 and comparative example 1 ~ 3, from its machined surface (surface), to the whole region of the thickness direction (corresponding to depth of corrosion) of sintered compact, measure ratio resistance by resistance measurement device.At this, make the niobium oxides sputtering target of diameter 152.4mm × thickness 10mm with aforesaid manufacture method, on depth of corrosion direction, till cutting 2mm, 4mm, 5mm, 6mm, 8mm from surface (0mm), measure ratio resistance herein.Above result is shown in Table 3.In addition, in comparative example 1 ~ 3, owing to going beyond the scope, be therefore set to " measurement range is outer ", afterwards owing to not measuring, therefore represent with "-".
Further, in surface (0mm), the ratio resistance at 5 places in target sputter face is as shown in Figure 1 measured.For direction in sputter face, calculate the maximum difference (difference of maximum and Schwellenwert) of each measuring point.Above result is shown in Table 4.In addition, in comparative example 1 ~ 3, owing to going beyond the scope, be therefore set to " measurement range is outer ", afterwards owing to not measuring, therefore represent with "-".
As this resistance measurement device, use the low-resistivity meter (Loresta-GP) of MitsubishiChemicalCorporation, carry out the mensuration of ratio resistance (Ω cm) with four probe method.Temperature during mensuration is 23 ± 5 DEG C, is 50 ± 20% to measure in humidity.
[table 3]
[table 4]
The mensuration > of < rate of film build
Use the niobium oxides sputtering target of embodiment 1 ~ the 9 and comparative example 1 ~ 3 obtained, implement the film forming of the niobium oxides film by sputtering, and measure rate of film build.
When sputtering, at DC power supply, target-substrate pitch from TS=70mm, the gas Ar used, air pressure 0.67Pa, under gas flow is fixed on the condition of 50sccm, by niobium oxide film film forming on substrate.Measure the thickness of the niobium oxides film of this film forming, calculate rate of film build (nm/sec).
Above result is shown in " sputtering characteristic " hurdle of table 5.
< could carry out the evaluation > of DC sputtering
To the niobium oxides sputtering target of obtained embodiment 1 ~ 9 and comparative example 1 ~ 3, could DC sputtering be carried out to evaluate, making the niobium oxides sputtering target of diameter 152.4mm × thickness 10mm with aforesaid manufacture method.
Be used in the niobium oxides sputtering target that this obtains, the distance TS=70mm between target-substrate, the gas Ar used, air pressure 0.67Pa, gas flow is under the condition of 50sccm, carries out continuous discharge by DC power supply.Further, till from the surface element (0mm) of niobium oxides sputtering target to corrosion portion (thickness direction, the part reamed because of sputtering), depth of corrosion carries out DC sputtering till becoming 2mm, 4mm, 5mm, 6mm, 8mm.
In each depth of corrosion, the situation that can proceed DC sputtering is set to "○", will not discharge, and paradoxical discharge frequently occurs, and the situation that cannot be suitable for DC sputtering is set to "×".In addition, for the situation cannot carrying out DC sputtering, be designated as "-".The results are shown in " evaluation (depth of corrosion) of DC sputtering could be carried out " hurdle of table 5.
[table 5]
According to the result shown in above each table, confirm the niobium oxides sputtering target of embodiment 1 ~ 9 all with the niobium oxides (Nb of oxygen damage condition 2o 5-x) form, and be dispersed with the higher Nb of electroconductibility 12o 29phase, and, the whole region at target thickness direction can be found out, ratio resistance is in the scope of 0.001 ~ 0.05 Ω cm, and the maximum difference of ratio resistance in this thickness direction can reach 0.02 below Ω cm, and the whole region in target sputter face, ratio resistance is in the scope of 0.001 ~ 0.05 Ω cm, and the maximum difference of ratio resistance can reach 0.02 below Ω cm in the face of this target sputter face.Therefore, can find out in the niobium oxides sputtering target of embodiment 1 ~ 9, in the whole region and sputter face of target thickness direction, due to target ratio resistance can be reduced equably, therefore not only can carry out stable DC sputtering all the time, and by reducing target ratio resistance, the rate of film build of sputtering can be improved.
On the other hand, in the niobium oxides sputtering target of comparative example 1 and 2, use commercially available niobium oxide powder (Nb as raw material powder 2o 5powder), and there is no reduction treatment and directly sinter, therefore in its sintered compact, only till the midway of thickness direction, generate the oxygen defect niobium oxides (Nb having the amount of the oxygen defect generated during sintering few 2o 5-x), especially there is not Nb 12o 29phase, therefore in the whole region and sputter face of target thickness direction, cannot reduce target ratio resistance equably.Further, in the niobium oxides sputtering target of comparative example 3, will to niobium oxide powder (Nb 2o 5powder) carry out the oxygen defect niobium oxide powder (Nb of reduction treatment 2o 5-xpowder) obtain sintered compact as raw material powder, but due to the reductive condition of reduction treatment, namely temperature is 300 DEG C, therefore rests on the oxygen defect niobium oxides (Nb that the amount that generates oxygen defect is few 2o 5-x) state, especially there is not Nb 12o 29phase, therefore in the whole region and sputter face of target thickness direction, cannot reduce target ratio resistance equably.The niobium oxides sputtering target of comparative example 1 ~ 3 all becomes and cannot carry out DC sputtering on the way, even if carry out DC sputtering, rate of film build also can not get improving.
[the 2nd embodiment]
In the 2nd embodiment of the present invention, the average crystallite particle diameter making the niobium oxides crystal grain in niobium oxides sintered compact is the niobium oxides sputtering target of less than 100 μm.
When making niobium oxides sputtering target, as an example, use the reducing powder of the embodiment 1 in above-mentioned 1st embodiment.As mentioned above, this reducing powder is to niobium oxide powder (Nb 2o 5powder) implement reduction treatment and become the niobium oxide powder (Nb of oxygen damage condition 2o 5-xpowder), the reducing powder of embodiment 10 ~ 14 shown in table 6.To embodiment 10 ~ 14, measured the oxygen defect amount of reducing powder by the step identical with the situation of the 1st embodiment.Oxygen defect amount x is obtained by above-mentioned calculation formula.The results are shown in " the reducing powder oxygen defect Nb of table 6 2o 5-x" in hurdle, because any reducing powder all uses the reducing powder of embodiment 1, therefore x=0.05.Further, also Nb is confirmed 12o 29the presence or absence of phase.
Next, this reducing powder and zirconia ball are added in plastic bottle (polyethylene bottle), use dry ball device, with the rotating speed of 80 ~ 120rpm mixing 1 ~ 3 hour.Then, by obtained Nb 2o 5-xthe sieve that powder is 32 ~ 600 μm by aperture carries out classification, becomes 2 ~ 100 μm to make median size.In " reducing powder median size (μm) " hurdle of table 6, the median size of the reducing powder of embodiment 10 ~ 14 is shown.
By the reducing powder (Nb so obtained 2o 5-xpowder) as raw material powder, by the mode identical with the situation of the 1st embodiment, this raw material powder is filled in mould, according to the sintering method shown in table 7 and sintering condition, under vacuum atmosphere, by keeping 2 ~ 3 hours at the temperature of 900 ~ 1200 DEG C, carrying out hot pressing (HP) with the pressure of 15 ~ 50MPa, making niobium oxides (Nb 2o 5-x) the sintered compact of embodiment 10 ~ 14.Further, mechanical workout will be carried out to this sintered compact, make the niobium oxides sputtering target with the embodiment 10 ~ 14 of diameter 152.4mm.
And, to the niobium oxides sputtering target of embodiment 10 ~ 14, by the step identical with the situation of the 1st embodiment, measure oxygen defect amount.Oxygen defect amount x is obtained by above-mentioned calculation formula.The results are shown in " the sintered compact oxygen defect Nb of table 7 2o 5-x" in hurdle.Further, by the mode identical with the situation of the 1st embodiment, the Nb of XRD is carried out 12o 29the presence or absence evaluation of phase, and " the sintered compact Nb being shown in table 7 12o 29the presence or absence of phase ".
Further, to the niobium oxides sputtering target of embodiment 10 ~ 14, niobium oxides crystallization particle diameter is measured.In this mensuration, 5 places in each niobium oxides sputtering target sample, use EBSD (ElectronBackScatterDiffractionPatterns), in the analytical data obtained by analytical equipment (TSL Inc. OIMdatacollection), measure crystallization particle diameter everywhere.Obtained each value is averaged, and as average crystallite particle diameter.The results are shown in " sintered compact average crystallite particle diameter (μm) " hurdle of table 7.
[table 6]
[table 7]
Next, to the niobium oxides sputtering target of obtained embodiment 10 ~ 14, by the mode identical with the situation of the 1st embodiment, from its machined surface (surface), to the whole region of the thickness direction (corresponding to depth of corrosion) of sintered compact, measure ratio resistance by resistance measurement device.By the niobium oxides sputtering target made with aforesaid manufacture method, on depth of corrosion direction, till cutting 2mm, 4mm, 5mm, 6mm, 8mm from surface (0mm), measure the ratio resistance at this place.Above result is shown in Table 8.And, for surface (0mm), measure the ratio resistance at 5 places in target sputter face as shown in Figure 1.To direction in sputter face, calculate the maximum difference (difference of maximum and Schwellenwert) of each measuring point.Above result is shown in Table 9.
[table 8]
[table 9]
Use the niobium oxides sputtering target of the embodiment 10 ~ 14 obtained, implement the film forming of the niobium oxides film by sputtering, and measure rate of film build.By the mode identical with the situation of the 1st embodiment, measure the thickness of the niobium oxides film of this film forming, and calculate rate of film build (nm/sec).The results are shown in " sputtering characteristic rate of film build (nm/sec) " hurdle of table 10.
And to the niobium oxides sputtering target of obtained embodiment 10 ~ 14, evaluation could sputter.By the mode identical with the situation of the 1st embodiment, use these niobium oxides sputtering targets, till from target surface element (0mm) to corrosion portion (thickness direction, the part reamed because of sputtering), depth of corrosion carries out DC sputtering till becoming 2mm, 4mm, 5mm, 6mm, 8mm.At this, in each depth of corrosion, the situation that can proceed DC sputtering is set to "○".The results are shown in " evaluation (depth of corrosion) of DC sputtering could be carried out " hurdle of table 10.
When carrying out above-mentioned DC sputtering, measure paradoxical discharge frequency during sputtering.Carry out the sputtering of 1 hour, to the frequency of differential of the arc paradoxical discharge, with the electric arc counter being attached to shielding power supply device, automatically measure its number of times.Further, will sputter target, from surface, become the moment of 2mm4mm6mm8mm in the degree of depth of erodable section, and also similarly carry out the sputtering of each 1 hour respectively, and measure the frequency of paradoxical discharge.This measurement result is shown in Table 11.
[table 10]
[table 11]
According to the result shown in above each table, the niobium oxides sputtering target confirming embodiment 10 ~ 14 is all identical with the niobium oxides sputtering target of embodiment 1 ~ 9, by the niobium oxides (Nb of oxygen damage condition 2o 5-x) form, and be dispersed with the higher Nb of electroconductibility 12o 29phase, and, the whole region at target thickness direction can be confirmed, ratio resistance is in the scope of 0.001 ~ 0.05 Ω cm, and the maximum difference of ratio resistance in this thickness direction can reach 0.02 below Ω cm, and the whole region in target sputter face, ratio resistance is in the scope of 0.001 ~ 0.05 Ω cm, and the maximum difference of ratio resistance can reach 0.02 below Ω cm in the face of this target sputter face, and, especially the average crystallite particle diameter confirming niobium oxides crystal grain is less than 100 μm, and the paradoxical discharge number of times that can also suppress when sputtering can be found out.Therefore, can find out in the niobium oxides sputtering target of embodiment 10 ~ 14, in the whole region and sputter face of target thickness direction, target ratio resistance can be reduced equably, and owing to reducing paradoxical discharge number of times, not only can carry out stable DC sputtering all the time, and by reducing target ratio resistance, the rate of film build of sputtering can be improved.
In addition, above-described 2nd embodiment is, use the situation of the reducing powder of the embodiment 1 in the 1st embodiment, but the 2nd embodiment is not limited to the situation of this embodiment 1, even if confirm used reducing powder to have chemical formula: Nb 2o 5-xwhen (wherein, x=0.005 ~ 0.1), also play above-mentioned effect.
In above content the shape of sintered compact is described with being not particularly limited, as long as but this sintered compact by oxygen defect niobium oxides (Nb of the present invention 2o 5-x) make, then in the whole region of its thickness direction, can realize lower ratio resistance, therefore its shape can be dull and stereotyped, also can be cylinder.More specifically, the shape of sintered compact can be tabular or the drum of disc plate shape, rectangular plate shape, polygonal panel shape and ellipse shape etc.
The thickness direction of so-called sintered compact or the thickness direction of sputtering target in this specification sheets, refer to the depth direction in the face of ionizable element collision when sputtering.
Utilizability in industry
When forming niobium oxides film, the rate of film build of sputtering can be improved, and the productivity of niobium oxides film can be improved.

Claims (11)

1. a niobium oxides sputtering target, it is niobium oxides sintered compact, it is characterized in that,
In the whole region of the thickness direction of described niobium oxides sintered compact, ratio resistance is 0.001 ~ 0.05 Ω cm.
2. niobium oxides sputtering target according to claim 1, is characterized in that,
The average crystallite particle diameter of the niobium oxides crystal grain in described niobium oxides sintered compact is less than 100 μm.
3. niobium oxides sputtering target according to claim 1 and 2, is characterized in that,
The maximum difference of the ratio resistance of the target thickness direction of described niobium oxides sintered compact is 0.02 below Ω cm, and the maximum difference of ratio resistance in sputter face is 0.02 below Ω cm.
4. the niobium oxides sputtering target according to any one of claims 1 to 3, is characterized in that,
Described niobium oxides sintered compact is by meeting chemical formula: Nb 2o 5-xniobium oxides form, wherein, x=0.005 ~ 0.1.
5. the niobium oxides sputtering target according to any one of Claims 1 to 4, is characterized in that,
Described niobium oxides sintered compact meets chemical formula by use: Nb 2o 5-xniobium oxide powder carry out sintering and obtaining, wherein, x=0.005 ~ 0.1.
6. the niobium oxides sputtering target according to any one of Claims 1 to 5, is characterized in that,
In the matrix of described niobium oxides sintered compact, be evenly distributed with Nb 12o 29phase.
7. a manufacture method for niobium oxides sputtering target, is characterized in that, has:
Reduction operation, carries out reduction treatment to obtain oxygen defect niobium oxide powder to niobium oxide powder;
Mixed processes, in order to reduce the oxygen level deviation of the oxygen defect niobium oxide powder obtained as required, mixes oxygen defect niobium oxide powder; And sintering circuit, under nonoxidizing atmosphere, sinter obtained oxygen defect niobium oxide powder to obtain sintered compact.
8. the manufacture method of niobium oxides sputtering target according to claim 7, is characterized in that,
In described reduction operation, heat-treat to niobium oxide powder with the temperature of more than 500 DEG C under reducing atmosphere, generate and meet chemical formula: Nb 2o 5-xthe niobium oxide powder of oxygen damage condition, wherein, x=0.005 ~ 0.1.
9. the manufacture method of the niobium oxides sputtering target according to claim 7 or 8, is characterized in that,
Before described sintering circuit, there is the mixed processes of the oxygen level deviation reducing described acquired oxygen defect niobium oxide powder.
10. the manufacture method of the niobium oxides sputtering target according to any one of claim 7 ~ 9, is characterized in that,
The crystallization particle diameter of described oxygen defect niobium oxide powder is less than 100 μm.
11. 1 kinds of niobium oxides films, is characterized in that,
Described niobium oxides film uses the niobium oxides sputtering target spatter film forming according to any one of claim 1 ~ 6.
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