KR102302021B1 - Sputtering target and manufacturing method of sputtering target - Google Patents

Abstract

This sputtering target has a metallic copper phase and a copper oxide phase, and the volume fraction of the copper oxide phase exceeds 80 vol% and falls within the range of 90 vol% or less, and as a result of X-ray photoelectron spectroscopy analysis, CuO peak intensity IP1 and characterized in that the non-IP1 / IP2 IP2 of the peak intensity of Cu and Cu ₂ O, is in the range of 0.03 or more to 0.4 or less.

Description

Sputtering target and manufacturing method of sputtering target

This invention relates to the sputtering target used when forming a copper oxide film, and the manufacturing method of a sputtering target.

This application claims priority based on Japanese Patent Application No. 2017-038578 for which it applied to Japan on March 1, 2017 and Patent Application No. 2018-024510 for which it applied to Japan on February 14, 2018, the content is here be invoked in

Generally, as a conductive film used for a touch sensor etc., what has the transparent conductor layer formed in both surfaces of a film, and the metal layer formed in the surface of each transparent conductor layer is known.

Here, in the above-mentioned electroconductive film, when it wound up in roll shape, adjacent electroconductive films closely_contact|adhered, and when the adhered electroconductive film was peeled off, there existed a problem that a flaw generate|occur|produced in a transparent conductor layer.

Therefore, Patent Document 1 proposes a film in which an inorganic nano-coating layer is formed on a film substrate. In this film, it becomes possible to suppress close_contact|adherence of adjacent films by an inorganic nano-coating layer. Moreover, a copper oxide film can be applied as this inorganic nano-coating layer.

As a method of forming a copper oxide film on the surface of a base material such as a film, for example, a method of performing sputtering using a copper oxide target, or a method of performing sputtering (reactive sputtering) using an oxygen-free copper target in the presence of oxygen gas A method is disclosed.

For example, Patent Document 2 proposes an oxygen-containing copper target for forming an oxygen-containing copper film.

Moreover, in patent document 3, the sputtering target which consists of Ni, Cu, and CuO is disclosed.

Japanese Patent Publication No. 2014-529516 Japanese Laid-Open Patent Publication No. 2008-280545 Japanese Patent Publication No. 5808513

However, when sputtering is performed in the presence of oxygen gas using an oxygen-free copper target, the reaction between copper and oxygen cannot be sufficiently controlled, and it is difficult to form a uniform copper oxide film.

Moreover, when a copper oxide target is used, since the resistance of target itself is very high and DC (direct current) sputtering is difficult, RF (high frequency) sputtering is performed normally. In this RF (high frequency) sputtering, there existed a problem that the film-forming speed|rate was slow and productivity fell.

Moreover, in the oxygen-containing copper target of patent document 2, since there was little content of oxygen, the oxygen-containing copper film formed into a film had the characteristic similar to a metallic copper film, and the characteristic as a copper oxide film was inadequate.

Moreover, in patent document 3, although sintering is performed by the electric current sintering method, when the content of CuO increases, the reaction of Cu and CuO does not fully advance, the intensity|strength of a sintered compact becomes insufficient, and there exists a possibility of cracking at the time of manufacture. there was Moreover, there exists a possibility that the dispersion|variation in specific resistance may arise in a sintered compact. Moreover, when Ni is contained, the etching property of a film|membrane deteriorated, and there existed a possibility that it might become difficult to form a wiring pattern etc. with high precision. Moreover, there existed a possibility that Ni was mixed in etching liquid other than Cu, and there existed a possibility that reuse of etching liquid might become difficult.

The present invention has been made in view of the circumstances described above, and a sputtering target capable of stably DC sputtering, suppressing crack generation at the time of target production, and producing with good yield, and a method for producing the sputtering target intended to provide

In order to solve the said subject, the sputtering target of this invention has a metallic copper phase and a copper oxide phase, The volume ratio of the said copper oxide phase exceeds 80 vol% and is in the range of 90 vol% or less, X-ray photoelectron spectroscopy the results of the analysis, and is characterized in that the peak intensity of CuO and Cu IP1 and IP2 peak intensity of Cu ₂ O is non-IP1 / IP2, it is within the range between 0.03 to 0.4.

According to the sputtering target of this invention, since the volume ratio of a copper oxide phase exceeds 80 vol%, even if a copper oxide phase fully exists and it does not sputter|spatter in oxygen gas presence, a copper oxide film can be formed into a film. Moreover, since the volume ratio of a copper oxide phase is in the range of 90 vol% or less, a specific resistance becomes low and it becomes possible to form a copper oxide film into a film by DC sputtering.

And, as a result of X-ray photoelectron spectroscopy, _{the ratio IP1/IP2 of the peak intensity IP1 of CuO and the peak intensity IP2 of Cu and Cu 2} O is 0.03 or more, and since CuO is present in the copper oxide phase, the strength of the sintered body can be improved, and crack generation at the time of manufacture can be suppressed. On the other hand, since the ratio IP1/IP2 of the peak intensity IP1 of CuO and _{the peak intensity IP2 of Cu and Cu 2} O is 0.4 or less, the abundance ratio of CuO does not increase too much in the copper oxide phase, and the resistance value in the target is deviation can be suppressed. Therefore, DC sputtering can be performed stably.

Here, in the sputtering target of the present invention, the results of X-ray diffraction analysis, it is preferred that the diffraction intensity ratio of CuO and IR1 IR1 / IR2 of the diffraction intensity IR2 of the Cu ₂ O less than or equal to 0.15.

In this case, the less the ratio of CuO in the oxidation ditch risang, a high existence ratio of Cu ₂ O. Here, CuO is not generated because the Cu ₂ O reacts with the copper metal, if the ratio of CuO is high, the metal copper as CuO is not fully reacted. Therefore, by the ratio of CuO in the oxidation ditch risang less than 0.15, it is possible uniformly Cu ₂ O is dispersed, it is possible to suppress a variation in resistance of the target, within.

The manufacturing method of the sputtering target of this invention is a manufacturing method of the sputtering target which has a metallic copper phase and a copper oxide phase, The volume ratio of the said copper oxide phase exceeds 80 vol% and is in the range of 90 vol% or less, At least Cu powder and a raw material powder preparation process of preparing a raw material powder containing and CuO powder, and a sintering process of sintering the raw material powder to obtain a sintered body, wherein the average particle diameter of the CuO powder is 3 µm or more, and the sintering temperature is 720 It is characterized in that it is not less than °C.

According to the manufacturing method of the sputtering target of this invention, Cu powder and CuO powder with an average particle diameter of 3 micrometers or more are used as raw material powder, Since the sintering temperature in a sintering process is set to 720 degreeC or more, Cu in a sintering process When CuO and CuO react to form Cu ₂ O, some CuO remains. Thus, there is a peak intensity of CuO and Cu and non-IP1 IP1 / IP2 IP2 of the peak intensity of Cu ₂ O can be adjusted to within the range of 0.4 or less than 0.03. Therefore, the intensity|strength of a sintered compact can be ensured and crack generation at the time of manufacture can be suppressed. Moreover, the dispersion|variation in specific resistance can be suppressed and DC sputtering can be performed stably.

ADVANTAGE OF THE INVENTION According to this invention, DC sputtering is possible stably, the sputtering target which can suppress generation|occurrence|production at the time of manufacture of a target, and can manufacture with favorable yield, and the manufacturing method of this sputtering target can be provided.

BRIEF DESCRIPTION OF THE DRAWINGS It is explanatory drawing which shows the measurement position of the resistance value in the target sputtering surface of the sputtering target whose target shape is a flat plate and the target sputtering surface forms a circle.
It is explanatory drawing which shows the measurement position of the resistance value in the target sputtering surface of the sputtering target whose target shape is a flat plate, and the target sputtering surface forms a rectangle.
It is explanatory drawing which shows the measurement position of the resistance value in the target sputtering surface of the sputtering target whose target shape is a cylinder and the target sputtering surface is a cylindrical outer peripheral surface.
It is a flowchart which shows the manufacturing method of the sputtering target which is this embodiment.
5 is a diagram showing an example of XPS results in Example 13 of the present invention.
It is a figure which shows an example of the XRD result in Inventive Example 2 and Comparative Example 1. FIG.

EMBODIMENT OF THE INVENTION Below, the sputtering target which is one Embodiment of this invention, and the manufacturing method of a sputtering target are demonstrated. In addition, the sputtering target which is this embodiment is used when forming a copper oxide film into a film.

The sputtering target which is this embodiment has a metallic copper phase and a copper oxide phase, The volume ratio of a copper oxide phase exceeds 80 vol%, and it exists in the range of 90 vol% or less. Moreover, in this embodiment, content of Cu exists in the range of 70 atomic% or more and 74 atomic% or less.

It is noted that, X-ray photoelectron spectroscopy (XPS) result, CuO of the peak intensity IP1 and Cu and non-IP1 / IP2 of the peak intensity IP2 of Cu ₂ O, the range of 0.03 or more to 0.4 or less in a sputtering target of this embodiment made into me That it is, in this embodiment, and is a copper oxide phase, Cu ₂ O as the main component, it is possible to CuO is present in the part.

Further, in the sputtering target of the present embodiment, the results of X-ray diffraction analysis (XRD), a diffraction intensity IR1 of CuO and non IR1 / IR2 of the diffraction intensity IR2 of the Cu ₂ O is less than 0.15. That it is, in this embodiment, but the existing ratio of CuO is not increased more than necessary in the oxidation ditch risang, so that the Cu ₂ O is present sufficiently.

And in the sputtering target which is this embodiment, it has the property of a p-type semiconductor as a whole target.

Moreover, the resistance value of the sputtering target which is this embodiment is 10 ohm*cm or less.

Moreover, in the sputtering target which is this embodiment, the dispersion|variation with respect to the average value of the resistance value in a target sputtering surface is 50 % or less.

Moreover, in the sputtering target which is this embodiment, the metallic copper phase is disperse|distributed to the island shape in the target, and the average particle diameter of the metallic copper phase is in the range of 10 micrometers or more and 200 micrometers or less.

Below, the volume ratio of the copper oxide phase in the sputtering target which is this embodiment, the diffraction intensity of X-ray diffraction analysis (XRD), the peak intensity of X-ray photoelectron spectroscopy (XPS), the dispersion|variation in resistance value, the average of metallic copper phase The reason why the particle size was defined as described above will be described.

(Volume ratio of copper oxide phase: more than 80 vol% and less than 90 vol%)

In the sputtering target which is this embodiment, the abundance ratio of a metallic copper phase and a copper oxide phase becomes especially important by forming a copper oxide film into a film by DC sputtering.

Here, when the volume ratio of the copper oxide phase is 80 vol% or less, there exists a comparatively large amount of metallic copper in the formed copper oxide film into a film, and there exists a possibility that the copper oxide film which has the characteristic as a copper oxide may become impossible to form into a film.

On the other hand, when the volume ratio of a copper oxide phase exceeds 90 vol%, the resistance value of the whole target rises and there exists a possibility that DC sputtering may become impossible. In this embodiment, the metallic copper phase is dispersed in an island phase, and the copper oxide phase existing between them reacts with the metallic copper phase and acts as a degenerate p-type semiconductor, so that the metallic copper phase is not sufficiently dispersed. Otherwise, it is thought that the overall resistance value of the target rises.

From such a reason, in this embodiment, the volume ratio of a copper oxide phase is set in the range of more than 80 vol% and 90 vol% or less.

Moreover, in order to form a film reliably of the copper oxide film excellent in a characteristic, it is preferable to make the volume ratio of a copper oxide phase into 85 vol% or more. On the other hand, in order to suppress the resistance value of a sputtering target further lower, it is preferable to make the volume ratio of a copper oxide phase into 85 vol% or less. That is, the volume ratio of a copper oxide phase exceeds 80 vol%, and it is within the range of 90 vol% or less WHEREIN: It is preferable to consider the characteristic or resistance value calculated|required, and to adjust the volume ratio of a copper oxide phase suitably.

(X-ray photoelectron spectroscopy (XPS) non-IP1 / IP2 of the peak intensity and Cu IP1 and IP2 of the peak intensity of CuO Cu ₂ O in 0.03 or less than 0.4)

When prepared by the sputtering target to the sintering, the Cu ₂ O is produced by the reaction of CuO with metal copper. _{Here, when the ratio IP1/IP of the peak intensity IP1 of CuO and the peak intensity IP2 of Cu and Cu 2} O in X-ray photoelectron spectroscopy (XPS) is less than 0.03, the strength of the sintered body is lowered, and cracks at the time of manufacture may occur. On the other hand, when IP1/IP exceeds 0.4, metallic copper and CuO do not fully react, the dispersion|variation in resistance value in a target becomes large, and there exists a possibility that DC sputtering may become impossible to perform stably.

_{From the above, in this embodiment, the ratio IP1/IP2 of the peak intensity IP1 of CuO and the peak intensity IP2 of Cu and Cu 2} O in X-ray photoelectron spectroscopy (XPS) is set within the range of 0.03 or more and 0.4 or less. . Moreover, in order to improve the intensity|strength of a sintered compact and to suppress the crack at the time of manufacture, it is preferable to set the lower limit of IP1/IP2 mentioned above to 0.05 or more, and it is more preferable to set it as 0.1 or more. Moreover, in order to suppress the dispersion|variation in resistance value and to suppress the generation|occurrence|production of an abnormal discharge, it is preferable to set the upper limit of IP1/IP2 mentioned above to 0.3 or less, and it is more preferable to set it as 0.2 or less.

In addition, since it is difficult to separate the peak _{of Cu and the peak of Cu 2} O in X-ray photoelectron spectroscopy (XPS), as shown in FIG. 5 , the peak intensity of _{Cu and Cu 2 O using IP2 CuO} stipulates the proportion of

(Ratio IR1/IR2 of CuO diffraction intensity IR1 and Cu ₂ O diffraction intensity IR2: 0.15 or less)

When prepared by sintering a sputtering target as described above, the Cu ₂ O is produced by the reaction of CuO with metal copper. Here, when a diffraction intensity of CuO and IR1 ratio IR1 / IR2 of the diffraction intensity IR2 of the Cu ₂ O less than or equal to 0.15, the ratio of CuO is lower, the metallic copper and the CuO is possible to sufficiently react. For this reason, the dispersion|variation in resistance value is suppressed in a target, and generation|occurrence|production of an abnormal discharge is suppressed.

From the above, in this embodiment, and sets the CuO of the diffraction intensity IR1 and non-IR1 / IR2 of the diffraction intensity IR2 of the Cu ₂ O to 0.15 or less. In addition, in order to reliably suppress the variation in resistance value and suppress the occurrence of abnormal discharge, _{the ratio IR1/IR2 of the diffraction intensity IR1 of CuO and the diffraction intensity IR2 of Cu 2} O is preferably 0.1 or less, and is 0.05 or less. It is more preferable to do

(Resistance value: 10 Ω·cm or less)

In order to perform DC sputtering stably, in the sputtering target which is this embodiment, it is preferable to make resistance value into 10 Ω·cm or less, and it is more preferable to set it as 1 Ω·cm or less.

In addition, let the resistance value of the sputtering target in this embodiment be the average value of the measured value in the some measurement point mentioned later.

(Deviation with respect to the average value of the resistance value on the target sputtering surface: 50% or less)

In the sputtering target which is this embodiment, electroconductivity is ensured by disperse|distributing a metallic copper phase, and DC sputtering becomes possible. Here, by making the dispersion|variation with respect to the average value of the resistance value in a target sputtering surface 50 % or less, a metallic copper phase will become disperse|distributed uniformly, and DC sputtering becomes possible stably. Moreover, generation|occurrence|production of the abnormal discharge at the time of sputtering can be suppressed.

From such a reason, in this embodiment, the deviation with respect to the average value of the resistance value in a target sputtering surface is set to 50 % or less. In addition, in order to uniformly disperse the metallic copper phase and ensure DC sputtering, it is preferable to make the variation with respect to the average value of the resistance values on the target sputtering surface 40% or less, and to set it to 30% or less more preferably.

Here, in this embodiment, when the shape of a sputtering target is a flat plate and a target sputtering surface forms a circle, as shown in FIG. 1, while passing through the center of a circle (1) and the center of a circle, mutually The resistance value is measured at 5 points of the outer peripheral parts (2), (3), (4), (5) of two orthogonal straight lines, and the deviation with respect to the average value of the resistance value in a target sputtering surface by the following formula are looking for In addition, the outer peripheral parts (2), (3), (4), (5) were made into the range within 10% of the diameter toward the inside from the outer peripheral edge.

In addition, when the shape of the sputtering target is a flat plate and the target sputtering surface forms a quadrangle, as shown in FIG. 2 , the intersection (1) where the diagonals intersect, the corners on each diagonal (2), (3), The resistance value is measured at 5 points|pieces of (4) and (5), and the deviation with respect to the average value of the resistance value in a target sputtering surface is calculated|required by the following formula. In addition, the corner parts (2), (3), (4), (5) were made into the range within 10% of the diagonal full length toward the inside from a corner part.

In addition, when the shape of the sputtering target is a cylinder and the target sputtering surface is a cylindrical outer circumferential surface, as shown in FIG. 3 , (1), (2), (1), (2), The resistance value is measured at the four points of (3) and (4), and the deviation with respect to the average value of the resistance value in a target sputtering surface is calculated|required by the following formula.

(deviation) % = standard deviation/mean × 100

(Mean particle size of metallic copper phase: 10 μm or more and 200 μm or less)

In this embodiment, since the average particle diameter of a metallic copper phase is comparatively fine at 200 micrometers or less, a metallic copper phase is disperse|distributed comparatively uniformly. Here, in the present embodiment, as described above, the metallic copper phase is dispersed in an island phase, and the copper oxide phase existing therebetween acts as a p-type semiconductor, so that the metallic copper phase is dispersed relatively uniformly. , electrical conductivity can be ensured in the whole target, and DC sputtering can be performed stably.

Moreover, when manufacturing the sputtering target which is this embodiment, although metallic copper powder is used, by prescribing|regulating the average particle diameter of a metallic copper phase to 10 micrometers or more, it is not necessary to make the particle size of metallic copper powder excessively fine, and a metal The oxidation of copper powder can be suppressed.

From the above, in this embodiment, the average particle diameter of a metallic copper phase is set in the range of 10 micrometers or more and 200 micrometers or less. In addition, in order to ensure the conductivity of the entire target and to perform DC sputtering more stably, the upper limit of the average particle diameter of the metallic copper phase is preferably 150 µm or less, and more preferably 100 µm or less. Moreover, in order to suppress oxidation of the metallic copper powder of a raw material reliably, it is preferable to set the lower limit of the average particle diameter of a metallic copper phase to 20 micrometers or more, and it is more preferable to set it as 30 micrometers or more.

(Manufacturing method of sputtering target)

Next, the manufacturing method of the sputtering target which is this embodiment is demonstrated with reference to the flowchart of FIG.

First, the raw material powder containing metal copper powder and copper oxide powder is prepared (raw material powder preparation process S01). Here, as a metallic copper powder, it is preferable to use the thing of purity 99.99% or more (4N) or more by mass ratio. Moreover, it becomes possible by adjusting the particle diameter of this metallic copper powder to control the average particle diameter of the metallic copper phase in a sputtering target. Specifically, it is preferable to make the average particle diameter of metallic copper powder into the range of 10 micrometers or more and 200 micrometers or less.

A copper oxide powder, and a mixed powder of the CuO powder and CuO powder and Cu ₂ O powder. CuO powder and Cu ₂ O powder is preferably used, the purity of Cu in the metal component greater than 99% (2 N) in a mass ratio. In addition, the average grain size of the Cu ₂ O powder is preferably in the range of less than 1 ㎛ 30 ㎛.

In addition, the average particle diameter of CuO powder shall be 3 micrometers or more. Moreover, although there is no restriction|limiting in the upper limit of the average particle diameter of CuO powder, It becomes 100 micrometers or less substantially.

In addition, with regard to the mixing amount of each of the powder, in the case of using a CuO powder in the copper oxide powder, the amount of the CuO powder is 36 mol% at least 44 mol% within the following range I preferably, the CuO powder and the Cu ₂ O powder to copper oxide powder If you are using, the total amount of CuO and Cu ₂ O powder, the powder is preferably less than 50 mol%.

The weighed metallic copper powder and copper oxide powder are mixed with a mixing device such as a ball mill, a Henschel mixer, and a rocking mixer to obtain a raw material powder. At this time, in order to prevent oxidation of metallic copper powder, it is preferable to make the atmosphere in a mixing apparatus into inert gas atmosphere, such as Ar.

Next, using the raw material powder mentioned above, it sinters by a hot press etc., and obtains a sintered compact (sintering process S02). In addition, it is preferable that the sintering temperature at this time be in the range of 720 °C or more and 900 °C or less, the holding time is in the range of 30 min or more and 600 min or less, and the pressurization pressure is in the range of 10 MPa or more and 50 MPa or less. In this sintering step S02, because the sintering temperature above 720 ℃, in response to the CuO and Cu ₂ O to form the Cu. In this embodiment, since the particle diameter of the CuO powder it is less than 3 ㎛, in response to the CuO and Cu may be formed with a Cu ₂ O is the remaining part of the CuO.

Next, the obtained sintered compact is machined (machining process S03). Thereby, the sputtering target which is this embodiment is manufactured.

In the sputtering target which is this embodiment which became the structure as mentioned above, since the volume ratio of a copper oxide phase exceeds 80 vol%, a copper oxide phase exists sufficiently and even if sputtering is not performed in oxygen gas presence, a copper oxide film can be filmed Moreover, since the volume ratio of a copper oxide phase is 90 vol% or less, electroconductivity as the whole target is ensured, and a copper oxide film can be formed into a film by DC sputtering.

And, in this embodiment, the sputtering target, as a result of X-ray photoelectron spectroscopic analysis, since the CuO peak intensity IP1 and Cu, and the peak intensity IP2 of Cu ₂ O is non-IP1 / IP2, is less than 0.03, the strength of the sintered body can be improved, and crack generation at the time of manufacture can be suppressed. Moreover, since IP1/IP2 is set to 0.4 or less, the abundance ratio of CuO in a copper oxide phase decreases, the dispersion|variation in the resistance value in a target can be suppressed, and DC sputtering can be performed stably.

In this embodiment, the result of X-ray diffraction analysis (XRD), in that the CuO of the diffraction intensity IR1 and ratio IR1 / IR2 of the diffraction intensity IR2 of the Cu ₂ O is less than 0.15, uniform as oxidation ditch risang Cu ₂ O becomes disperse|distributed and the dispersion|variation in the resistance value in a target can be suppressed. Therefore, a copper oxide film can be stably formed into a film by DC sputtering.

In addition, in this embodiment, a metallic copper phase is dispersed in an island phase, and the copper oxide phase existing between these metallic copper phases reacts with a metallic copper phase and acts as a degenerate p-type semiconductor, so that the property of a p-type semiconductor as a target as a whole. It is thought that conductivity is secured. Therefore, a copper oxide film can be formed into a film by DC sputtering.

Moreover, in this embodiment, since the resistance value of a sputtering target is 10 ohm*cm or less, DC sputtering can be performed reliably.

Moreover, in this embodiment, since the deviation with respect to the average value of the specific resistance value in a target sputtering surface is 50 % or less, electroconductivity becomes fully ensured as the whole target, and a copper oxide film is stably formed into a film by DC sputtering. it becomes possible to

Moreover, in the sputtering target which is this embodiment, since a density is 5.5 g/cm<3> or more, generation|occurrence|production of the abnormal discharge at the time of sputtering can be suppressed. On the other hand, since a density is 7.5 g/cm<3> or less, workability is ensured and this sputtering target can be shape|molded favorably.

Moreover, in the sputtering target which is this embodiment, since the average particle diameter of a metallic copper phase is 200 micrometers or less, when a metallic copper phase is finely disperse|distributed in a target, electroconductivity can be ensured to the whole target. Thereby, DC sputtering can be implemented stably. On the other hand, since the average particle diameter of the metallic copper phase is 10 µm or more, it is not necessary to make the particle size of the metallic copper powder excessively small at the time of target production, oxidation of the metallic copper powder can be suppressed, and sintering is performed favorably can do.

Also, when according to the production process of the present embodiment it is a sputtering target, because the average particle diameter of the CuO powder included in the material powder is more than 3 ㎛, and the Cu and CuO reaction in the sintering step S02 Cu ₂ O is produced it is possible to a residual CuO, it can be adjusted to a peak intensity IP1 and Cu and the above-mentioned range of non-IP1 / IP2 IP2 of the peak intensity of Cu ₂ O in CuO. That is, since the particle diameter of CuO powder is comparatively large, reaction of Cu and CuO does not advance in a short time, but it becomes possible to make CuO remain|survive.

In addition, since setting the sintering temperature in the sintering step S02 above 720 ℃, it can produce Cu ₂ O to securely reacting Cu and CuO.

As mentioned above, although embodiment of this invention was described, this invention is not limited to this, It can change suitably in the range which does not deviate from the technical idea of the invention.

Example

Hereinafter, the result of the confirmation experiment performed in order to confirm the effectiveness of this invention is demonstrated.

(sputtering target)

As raw material powder, metallic copper powder (purity: 99.9 mass% or more, average particle diameter is described in Table 1), CuO powder (purity of Cu in metal component: 99 mass% or more, average particle diameter is described in Table 1), Cu ₂ O powder (purity of Cu in the metal component: 99 mass% or more, average particle diameter 3 µm) was prepared.

These raw materials are weighed so as to have a mol ratio as shown in Table 1, and the weighed raw materials and zirconia balls (diameter: 5 mm) three times the weight of these raw materials are put into a container of a ball mill device in an Ar gas atmosphere. , and mixed for 3 hours.

After classifying the obtained raw material powder through a sieve, it was filled into a flat plate and a cylindrical mold of a hot press, and under a pressure of 20 MPa, at the sintering temperature shown in Table 1, the flat plate shape was maintained for 3 hours and the cylindrical shape was maintained for 5 hours.

The obtained sintered compact was machined, and the sputtering target for evaluation (plate shape: 126 mm x 178 mm x 6 mm, cylindrical shape: (phi 155 mm - phi 135 mm) x 150 mmL) was manufactured. And the following items were evaluated. The evaluation results are shown in Tables 1 and 2.

(volume ratio of copper oxide phase in target)

The copper concentration (atomic%) in the target is measured by a titration method, and the remainder is calculated as oxygen. It assumed that the calculated total amount of oxygen is present in the form of Cu ₂ O, and the volume was calculated and the rate of copper. In addition, since voids are not considered, the volume ratio here excludes voids.

(Average particle size of metallic copper phase in target)

The size was confirmed from the IQ map obtained by EBSD with respect to the metallic copper phase particle|grains in the structure|tissue of a sputtering target. In addition, the IQ map observed a cross-sectional range of 500 µm × 750 µm to quantitatively measure the particle size.

In addition, for EBSD, patterns were collected using OIM Data Collection of TSL Solutions, Inc., and particle size was calculated using OIM Analysis 5.31 manufactured by the company.

(density)

The density was calculated from the weight and dimensions of the sputtering target.

(X-ray photoelectron spectroscopy)

X-ray photoelectron spectroscopy (XPS) was performed under the following conditions. Further, the measurement surface of the measurement sample was surface polished with abrasive paper #2000, and Ar sputtering was performed from the outermost surface for analysis. In addition, this measurement was performed 20 minutes after the start of sputtering, and the data of Cu2p3/2 spectrum was used. An example of the analysis result is shown in FIG.

Device: ULVAC-PHI PHI5000 VersaProbeII

X-ray source: Monochromated AlKα 50 W

Pass Energy: 187.85 eV (Survey), 46.95, 58.7 eV (Profile)

Measurement interval: 0.8 eV/step (Survey), 0.1, 0.125 eV/step (Profile)

Photoelectron extraction angle with respect to the sample plane: 45 deg

Analysis area: about 200 μmφ

(X-ray diffraction analysis)

X-ray diffraction analysis (XRD) was performed under the following conditions. In addition, the calculation of the intensity ratio was calculated from the intensity of the 111 plane of CuO IR1, the intensity of the 200 plane of the Cu ₂ O as IR2. An example of the analysis result is shown in FIG.

Preparation of the sample: The sample was polished with SiC-Paper (grit 180), and was then used as a measurement sample.

Device: manufactured by Rika Electric (RINT-Ultima/PC)

Province: Cu

Tube voltage: 40 kV

Tube current: 40 mA

Scanning range (2θ): 5° to 80°

Slit size: Divergence (DS) 2/3 degree, Scattering (SS) 2/3 degree, light reception (RS) 0.8 mm

Measuring step width: 0.02 degrees in 2θ

Scan speed: 2 degrees per minute

Sample table rotation speed: 30 rpm

(cracks during manufacturing)

20 sputtering targets were manufactured on the conditions mentioned above, and the number of sheets in which cracks arose at that time was counted.

(target resistance value)

About the sputtering target, the resistivity was measured with the resistance measuring apparatus. In the case of a flat plate shape, with respect to the measurement points of five points (1 to 5) in the target sputtering surface as shown in Figs. 1 and 2, in the case of a cylindrical shape, 4 points (1 to 5) in the target sputtering surface as shown in Fig. 3 For the measurement point of 4), the resistivity was measured. Table 2 shows the average values of the measured in-plane resistivity. In this measurement, the resistivity (ohm*cm) was measured by the 4 probe method using the Mitsubishi Chemical Corporation low resistivity meter (Loresta-GP) as a resistance measuring apparatus. The temperature at the time of measurement was measured at 23±5°C, and the humidity was measured at 50±20%.

(deviation) % = standard deviation/mean × 100

(pn judgment)

About the sputtering target, pn determination was performed with the pn determination machine. In the case of a flat plate shape, with respect to a measurement point of one point 1 in the target sputtering surface as shown in Figs. 1 and 2, in the case of a cylindrical shape, a measurement point of one point 1 in the target sputtering surface as shown in FIG. , pn was determined. Table 2 shows the determined results. In this measurement, pn determination was performed with a thermoelectric probe using a pn determination machine (MODEL PN-01) manufactured by NPS Co., Ltd. as a pn determination machine. The temperature at the time of measurement was measured at 23±5°C, and the humidity was measured at 50±20%.

(Number of abnormal discharges)

About the obtained sputtering target, if it was flat, it bonded to a backing plate, if it was cylindrical, it bonded to a backing tube, and the frequency|count of abnormal discharge generation|occurrence|production at the time of sputtering was measured by the following procedure.

In the flat sputtering target, the film-forming test was implemented by the following film-forming conditions.

Target size: 126 mm × 178 mm × 6 mm

Power: DC 600 W

Voltage: 0.4 Pa

Sputtering gas: Ar = 50 sccm

Target-to-substrate (TS) distance: 70 mm

Moreover, in the cylindrical sputtering target, the film-forming test was implemented by the following film-forming conditions.

Target size: (φ155 mm-φ135 mm) × 150 mmL (4 divisions)

Power: DC 2000 W

Voltage: 0.4 Pa

Sputtering gas: Ar = 160 sccm

Target-to-substrate (TS) distance: 60 mm

Sputtering for 1 hour was performed in the said film-forming conditions, and the frequency|count of occurrence of abnormal discharge was automatically counted with the arcing counter attached to the sputtering power supply apparatus.

(membrane resistance value)

In this measurement, the sheet resistance (Ω/□ (square)) was measured by a four-probe method using a low resistivity meter (Loresta-GP) manufactured by Mitsubishi Chemical Corporation as a resistance measuring device. The temperature at the time of measurement was measured at 23±5° C., and the humidity was measured at 50±20%.

The sample used for the measurement was produced under the sputtering conditions mentioned above. The film was formed into a film with a target film thickness of 200 nm on the glass substrate.

In Comparative Example 1 and Comparative Example 3 in which the volume fraction of the copper oxide phase exceeded 90 vol%, resistance value was high and DC sputtering was not able to be performed.

In Comparative Example 2 and Comparative Example 4 in which the volume fraction of the copper oxide phase was 80 vol% or less, the resistance value of the formed copper oxide film was low, and the characteristic as a copper oxide film was inadequate.

Further, as a result of X-ray photoelectron spectroscopy, in Comparative Examples 3, 4, and 6-9 in which the ratio IP1/IP2 _{of the peak intensity IP1 of CuO and the peak intensity IP2 of Cu and Cu 2 O was less than 0.03, at the time of production} There were many occurrences of cracks in the Moreover, in Comparative Examples 3, 4, and 7-9, since CuO powder was not used as a raw material, IP1/IP2 was 0. Moreover, in the comparative example 6, since the average particle diameter of CuO powder was as small as 2 micrometers, CuO did not fully remain|survive, but IP1/IP2 was 0.02.

Further, in the peak intensity of CuO IP1 and Comparative Example 5 that the non-IP1 / IP2 of Cu and IP2 peak intensity of Cu ₂ O exceeds 0.4, an increased variation in the resistance value. Moreover, the frequency|count of generation|occurrence|production of abnormal discharge was large, and DC sputtering could not be carried out stably. In this comparative example 5, since the sintering temperature in a sintering process was as low as 580 degreeC, it is estimated that it is because reaction of Cu and CuO was insufficient.

On the other hand, as a result of X-ray photoelectron spectroscopy analysis _{, according to Inventive Example 1-14, the ratio IP1/IP2 of the peak intensity IP1 of CuO and the peak intensity IP2 of Cu and Cu 2} O was in the range of 0.03 or more and 0.4 or less. It was confirmed that crack generation|occurrence|production of the time was suppressed. Moreover, it was confirmed that the resistance value was low, DC sputtering was possible, and the copper oxide film excellent in a characteristic could be formed into a film.

Claims (3)

It has a metallic copper phase and a copper oxide phase, wherein the metallic copper phase is dispersed in an island form in the target, and the volume fraction of the copper oxide phase exceeds 80 vol% and falls within the range of 90 vol% or less,
X-ray results of photoelectron spectroscopy, CuO of the peak intensity IP1 and Cu and non-IP1 / IP2 IP2 of the peak intensity of Cu ₂ O, the sputtering target, characterized in that it is in the range of less than 0.03 to 0.4. The method of claim 1,
X-ray diffraction analysis result of the sputtering target, characterized in that the diffraction intensity IR1 of CuO and the ratio IR1 / IR2 of the diffraction intensity IR2 of the Cu ₂ O less than or equal to 0.15. A method for producing a sputtering target having a metallic copper phase and a copper oxide phase, wherein the volume ratio of the copper oxide phase exceeds 80 vol% and falls within the range of 90 vol% or less,
A raw material powder preparation step of preparing a raw material powder containing at least Cu powder and CuO powder, and a sintering process of sintering the raw material powder to obtain a sintered body,
The average particle diameter of the said CuO powder shall be 3 micrometers or more, and the sintering temperature shall be 720 degreeC or more, The manufacturing method of the sputtering target characterized by the above-mentioned.

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