PALLADIUM COBALT OXIDE THIN FILM, DELAFOSSITE-TYPE OXIDE THIN FILM, SCHOTTKY ELECTRODE HAVING DELAFOSSITE-TYPE OXIDE THIN FILM, METHOD FOR PRODUCING PALLADIUM COBALT OXIDE THIN FILM, AND METHOD FOR PRODUCING DELAFOSSITE-TYPE OXIDE THIN FILM
20260011560 ยท 2026-01-08
Assignee
- NATIONAL INSTITUTE FOR MATERIALS SCIENCE (Tsukuba-shi, Ibaraki, JP)
- TANAKA PRECIOUS METAL TECHNOLOGIES Co., Ltd. (Chuo-ku, Tokyo, JP)
Inventors
Cpc classification
H10P95/00
ELECTRICITY
C23C14/3414
CHEMISTRY; METALLURGY
International classification
C23C14/54
CHEMISTRY; METALLURGY
Abstract
A palladium cobalt oxide thin film, a delafossite-type oxide thin film, a Schottky electrode having a delafossite-type oxide thin film, a method for producing a palladium cobalt oxide thin film, and a method for producing a delafossite-type oxide thin film are provided. In the palladium cobalt oxide thin film, the crystal grain size in the film is 100 nm or more and 500 nm or less, the thickness is greater than the critical film thickness, and the roughness value in the thickness direction is 4 nm or less.
Claims
1. A palladium cobalt oxide thin film, wherein a crystal width in the film is 100 nm or more and 1000 nm or less, a film thickness is greater than a critical film thickness, and a roughness value in a thickness direction is 4 nm or less.
2. The palladium cobalt oxide thin film according to claim 1, wherein an electrical resistivity is 6 cm or less at absolute temperatures from 2 K to 150 K, and the electrical resistivity at absolute temperatures from 150 K to 400 K satisfies the following formula (1):
3. The palladium cobalt oxide thin film according to claim 1, wherein palladium cobalt oxide thin film does not contain metal palladium crystals or tricobalt tetroxide.
4. The palladium cobalt oxide thin film according to claim 1, wherein the film thickness is 20 nm or less.
5. A delafossite-type oxide thin film comprising palladium chromium oxide (PdCrO.sub.2), palladium rhodium oxide (PdRhO.sub.2), or platinum cobalt oxide (PtCoO.sub.2) having a delafossite-type crystal structure, wherein a crystal width in the film is 100 nm or more and 1000 nm or less, a film thickness is greater than a critical film thickness, and a roughness value in a thickness direction is 4 nm or less.
6. A Schottky electrode comprising a delafossite-type oxide thin film of palladium cobalt oxide (PdCoO.sub.2), palladium chromium oxide (PdCrO.sub.2), palladium rhodium oxide (PdRhO.sub.2), or platinum cobalt oxide (PtCoO.sub.2), wherein a crystal grain size in the film is 100 nm or more and 1000 nm or less, a film thickness is greater than a critical film thickness, and a roughness value in a thickness direction is 4 nm or less.
7. A method for producing a palladium cobalt oxide thin film comprising: a target production step of firing a mixed powder of palladium chloride (PdCl.sub.2), palladium (Pd), and lithium cobalt oxide (LiCoO.sub.2) to produce a target of palladium cobalt oxide (PdCoO.sub.2); a film deposition step of forming a thin film by sputtering using the target; and an annealing step of heat-treating the thin film.
8. The method for producing a palladium cobalt oxide thin film according to claim 7, wherein the annealing step comprises heat-treating the thin film at a temperature from 600 C. to 800 C.
9. A method of forming a delafossite-type oxide thin film comprising: a film deposition step of forming a thin film by sputtering using a target made of a delafossite-type oxide of palladium cobalt oxide (PdCoO.sub.2), palladium chromium oxide (PdCrO.sub.2), palladium rhodium oxide (PdRhO.sub.2), or platinum cobalt oxide (PtCoO.sub.2); and an annealing step of heat-treating the thin film.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
[0027] In the accompanying drawings:
[0028]
[0029]
[0030]
[0031]
[0032]
[0033]
DETAILED DESCRIPTION
[0034] A palladium cobalt oxide thin film, a delafossite-type oxide thin film, a Schottky electrode having a delafossite-type oxide thin film, a method for producing a palladium cobalt oxide thin film, and a delafossite-type oxide thin film according to an embodiment of the present disclosure will be described with reference to the drawings.
[0035] The delafossite-type oxide thin film according to the present embodiment is a delafossite-type oxide thin film of palladium cobalt oxide (PdCoO.sub.2), palladium chromium oxide (PdCrO.sub.2), palladium rhodium oxide (PdRhO.sub.2), or platinum cobalt oxide (PtCoO.sub.2) having a delafossite-type crystal structure. In the following, a palladium cobalt oxide thin film (PdCoO.sub.2 thin film, hereinafter sometimes simply referred to as oxide thin film), that is, a thin film made of palladium cobalt oxide having a delafossite-type crystal structure, will be exemplified and described as an example of the delafossite-type oxide thin film according to the present embodiment. The following description similarly applies when palladium cobalt oxide having a delafossite-type crystal structure is replaced with palladium chromium oxide, palladium rhodium oxide, or platinum cobalt oxide, each also having a delafossite-type crystal structure. Specifically, palladium cobalt oxide is represented by the general formula ABO.sub.2, where A is Pd and B is Co. Therefore, for the description regarding the palladium chromium oxide thin film, palladium rhodium oxide thin film, or platinum cobalt oxide thin film and their production methods, the elements Pd and Co in the description of the palladium cobalt oxide thin film and their production method (including descriptions related to the precursors and raw materials of palladium cobalt oxide) can simply be replaced by the corresponding elements A and B for palladium chromium oxide, palladium rhodium oxide, or platinum cobalt oxide.
[0036]
[0037] As illustrated in
[0038] As one example, the oxide thin film according to the present embodiment can be produced by a production method that includes a target production step of firing a mixed powder of palladium chloride (PdCl.sub.2) powder, palladium (Pd) powder, and lithium cobalt oxide (LiCoO.sub.2) powder to produce a PdCoO.sub.2 target; a film deposition step of forming a thin film by sputtering using this target; and an annealing step of heat-treating the formed thin film.
[0039] The target production step is the step of producing a PdCoO.sub.2 target to be used in the film deposition step. Before conducting the target production step, a mixing step is initially performed wherein powders of palladium chloride (PdCl.sub.2), palladium (Pd), and lithium cobalt oxide (LiCoO.sub.2) are mixed to form a mixed powder. In the target production step, the mixed powder is fired, and sintered and molded, if required, to produce a PdCoO.sub.2 target.
[0040] During the firing of the above-described mixed powder, cations are exchanged according to the reaction shown in the following formula (a), resulting in the synthesis of PdCoO.sub.2 (so-called cation exchange reaction method).
##STR00001##
[0041] The particle size of the PdCl.sub.2 powder, Pd powder, and LiCoO.sub.2 powder used to produce the mixed powder may be, for example, about a few micrometers to around 100 m, as measured in images observed under an SEM.
[0042] The firing in the target production step is performed at a firing temperature of 500 C. or higher and 900 C. or lower. Preferably, the firing in the target production step is performed at 550 C. or higher and 800 C. or lower. Firing at such firing temperatures allows for the production of PdCoO.sub.2 in powder form while improving the yield. Furthermore, in the target production step, it is desirable to carry out the firing such that the particle size of the fired PdCoO.sub.2 is 0.1 m or more and 50 m or less. The particle size of the fired PdCoO.sub.2 powder is 0.1 m or more and 30 m or less, as measured in an image observed under an SEM. The particle size of the fired PdCoO.sub.2 powder as described above enhances the tightness of the target after molding, which will be described later, thereby improving the handleability of the target.
[0043] The firing in the target production step may be performed under reduced pressure, at atmospheric pressure, or in a high oxygen partial pressure environment. When the firing is performed under reduced pressure, it may be conducted under a reduced pressure of 750 mTorr in an Ar atmosphere, for example. Performing the firing in a high oxygen partial pressure environment may sometimes suppress the decomposition of the fired powder into Pd or CoOx (where x is a positive value).
[0044] The above-described target production step can produce a target of PdCoO.sub.2 with relatively high purity.
[0045] The target production step may comprise conducting a molding step after the above-described firing to further sinter and mold the fired powder into a disk shape. In the molding step, the fired powder may be sintered while applying a pressure of 30 MPa or higher and 70 MPa or lower at a temperature of 550 C. or higher and 800 C. or lower. Preferably, in the molding step, the fired powder is sintered while applying a pressure of 45 MPa or higher and 55 MPa or lower at a temperature of 650 C. or higher and 750 C. or lower. This can produce a disk-shaped target with good handleability.
[0046] In the target production step, the PdCoO.sub.2 obtained by firing may be molded into a target for sputtering. For example, the above-described method for producing a target may not require pulverization of the synthesized PdCoO.sub.2 or additional molding.
[0047] The target production step may comprise performing ethanol washing and acid washing of the fired powder after firing. Ethanol washing and acid washing of the fired powder can remove lithium chloride and other impurities. Ethanol washing removes lithium chloride, while acid washing removes unreacted Pd powder (metal palladium). Nitric acid (e.g., with a concentration of 60 weight %) may be used for acid washing, for example.
[0048] The target production step may comprise pulverizing the fired powder as necessary to adjust the particle size of the fired powder. For example, adjusting the particle size of the fired powder to the order of several micrometers may improve the tightness of the target after molding as described later.
[0049] The film deposition step is a step of forming a PdCoO.sub.2 thin film using the target produced in the target production step by sputtering.
[0050] One example of preferred sputtering in the film deposition step is RF sputtering where a radio frequency alternating voltage is applied to the target and the chamber housing the target.
[0051] The sputtering conditions for forming a PdCoO.sub.2 thin film using RF sputtering in the film deposition step are as follows. The oxygen partial pressure during sputtering is 50 mTorr or higher and 250 mTorr or lower, preferably 80 mTorr or higher and 120 mTorr or lower. The substrate temperature during sputtering is 500 C. or higher and 800 C. or lower, preferably 550 C. or higher and 700 C. or lower. As a substrate for forming the PdCoO.sub.2 thin film, an Al.sub.2O.sub.3 (0001) substrate, i.e., a sapphire substrate (using the (0001) plane), can be used, for example.
[0052] By conducting the film deposition step as described above, a thin film with large crystal grains of PdCoO.sub.2 can be obtained even when a film with a thickness of 20 nm or less is formed, for example. Additionally, this thin film has a high flatness, the crystals are oriented along the c-axis, and the crystallinity is high.
[0053] The thin film formed in the film deposition step is subsequently subjected to an annealing step for heat treatment. This heat treatment allows for the production of a PdCoO.sub.2 thin film that contains no metal palladium and has a low electrical resistivity. Furthermore, this PdCoO.sub.2 thin film exhibits high crystallinity.
[0054] In the present embodiment, the phrase not containing metal palladium or tricobalt tetroxide (Co.sub.3O.sub.4) in the PdCoO.sub.2 thin film refers to the following. For example, when the intensities of the X-ray diffraction peaks corresponding to the diffraction angle of the (111) plane of metal palladium (40.1) or the diffraction angle corresponding to the (222) plane of Co.sub.3O.sub.4 (about) 38.6, observed by X-ray diffraction (XRD) is compared with the intensity of the X-ray diffraction peak corresponding to the diffraction angle of the (0006) plane of PdCoO.sub.2 (30.2), the intensities of the peaks corresponding to the diffraction angles of the (111) plane of metal palladium and the (222) plane of Co.sub.3O.sub.4 (about) 38.6 are 1/100 or less of the intensity of the X-ray diffraction peak corresponding to the (0006) plane of PdCoO.sub.2.
[0055] The heat treatment in the annealing step is conducted at a temperature of 600 C. or higher and 800 C. or lower, preferably 650 C. or higher and 700 C. or lower. This allows for the appropriate production of a PdCoO.sub.2 thin film that has a low electrical resistivity and does not contain metal palladium.
[0056] The oxide thin film according to the present embodiment is preferably formed to 1 nm or more and 20 nm or less. Such an oxide thin film is suitable for use as a Schottky electrode.
[0057] In the above description, the delafossite-type oxide thin film, the Schottky electrode having a delafossite-type oxide thin film, and the method for producing a delafossite-type oxide thin film have been described using the palladium cobalt oxide thin film as an example. However, as mentioned in the introduction, the description using the palladium cobalt oxide thin film as an example also applies similarly to a palladium chromium oxide thin film, a palladium rhodium oxide thin film, or a platinum cobalt oxide thin film. Furthermore, the methods for producing these thin films and Schottky electrodes including these thin films are similar to the method for producing a palladium cobalt oxide thin film and the Schottky electrode including the palladium cobalt oxide thin film.
EXAMPLES
Example 1
[0058] A palladium cobalt oxide thin film according to Example 1 was produced as follows.
[0059] Powdered PdCl.sub.2 (manufactured by Tanaka Precious Metals Co. Ltd., Pd chloride crystal), powdered Pd (manufactured by Tanaka Precious Metals Co. Ltd., Pd powder with a Pd purity higher than 99.9%), and powdered LiCoO.sub.2 (manufactured by Sigma-Aldrich, lithium cobalt oxide (III)) were weighed out 8.99 g, 5.39 g, and 9.92 g, respectively. They were mixed for 10 minutes in a mortar to obtain a mixed powder. The particle size of the LiCoO.sub.2 powder was in the range of about several micrometers to a dozen or so micrometers, as measured in images observed under an SEM.
[0060] Next, the mixed powder was vacuum-sealed (at about 10.sup.5 Torr) in a quartz tube, and the quartz tube was placed in a retention tube made of mullite. The retention tube was placed in a firing furnace equipped with a core tube made of mullite. The core tube of the firing furnace was controlled to maintain a temperature of 800 C., and the mixture was fired for 48 hours. The powder containing PdCoO.sub.2 was then recovered from the quartz tube.
[0061] The powder containing PdCoO.sub.2 was washed with ethanol to remove lithium chloride (ethanol washing), followed by washing with nitric acid (at a concentration of 60 weight %) to remove unreacted Pd (acid washing), to yield PdCoO.sub.2 powder. The recovered PdCoO.sub.2 powder weighed 17.58 g. In the ethanol washing, the powder containing PdCoO.sub.2 was stirred in ethanol for one hour. In the acid washing, the powder was stirred in nitric acid for four hours. The particle size of the PdCoO.sub.2 powder, as measured in an image observed under an SEM, approximately ranged from about 1 m to 50 m.
[0062] Next, the PdCoO.sub.2 powder was packed into a molding die and sintered by hot-press sintering under pressure to produce a processed disk-shaped target. The pressure during sintering (the pressure applied to the powder) was set to 50 MPa. The temperature inside the sintering furnace during sintering was maintained at 700 C. for 60 minutes. The sintering furnace was kept under a vacuum atmosphere.
[0063] Then, a PdCoO.sub.2 thin film was formed by RF sputtering using the disk-shaped target obtained as described above. Considering handling in the sputtering apparatus, the target was affixed to a copper backing plate (with a diameter of 50.8 mm and a thickness of 2 mm) and placed inside the chamber of the sputtering apparatus. The substrate used to form a thin film was an Al.sub.2O.sub.3 (0001) substrate (hereinafter referred to simply as the substrate). Upon sputtering, the chamber atmosphere was set to an oxygen-to-argon ratio of 2:1 at a pressure of 150 m Torr (with an oxygen partial pressure in the chamber of 100 mTorr), and the substrate temperature was set to 700 C. The RF power output was set to 100 W, and the frequency to 13.56 MHz. The target film thickness of the PdCoO.sub.2 thin film was 15 nm. The PdCoO.sub.2 thin film formed by sputtering was evaluated by X-ray diffraction.
[0064] The substrate having the PdCoO.sub.2 thin film formed thereon as described above was placed in a heating furnace set at 800 C., heat-treated at atmospheric pressure for 12 hours, and then removed from the furnace to yield a palladium cobalt oxide thin film according to Example 1. In the following description, the term thin film refers to the thin film after heat treatment.
[0065] The film thickness of the thin film was measured, the surface flatness was observed by AFM, and the thin film was subjected to X-ray diffraction and a measurement of the electrical resistivity.
[0066] The film thickness of the thin film was 15 nm. The interval of interference fringes near the PdCoO.sub.2 (0006) diffraction point was measured using X-ray diffraction, and the film thickness was determined based on the measurement.
[0067] The observation results of the surface morphology of the thin film by AFM (AFM topographic image) are as discussed previously with reference to
[0068] The AFM topographic image illustrated in
[0069]
[0070] Next, the thin film was evaluated by X-ray diffraction.
[0071] As described above,
[0072] Similarly to
[0073]
[0074] As illustrated in
[0075] Additionally, the electrical resistivity of the thin film in Example 1 from absolute temperatures of 2 K to 400 K satisfies the following equation (1):
where R (cm) represents the electrical resistivity and T (K) represents the absolute temperature.
[0076] As described above, the thin film in Example 1 demonstrated low electrical resistivity and high electrical conductivity even with a reduced film thickness. Given that the electrical resistivity of platinum is 9.81 cm at an absolute temperature of 273 K and 13.6 cm at 373 K, the thin film in Example 1 exhibited high electrical conductivity comparable to that of elemental metals even with a small film thickness of 20 nm or less, such as 15 nm. Therefore, the thin film is considered highly suitable for Schottky electrode applications, for example, when combined with gallium oxide. Such a high electrical conductivity observed in the thin film in Example 1 is believed to be attributable to the fact that, as indicated in the surface morphology results in
[0077] Additionally, the thin film in Example 1 did not contain metal palladium or other impurities, and it is considered to be produced with high reproducibility. Moreover, the lack of impurities ensures that when used in Schottky electrode applications in combination with materials such as gallium oxide, the thin film can achieve both heat resistance and reliability even in high-power applications, for example, without compromising the high thermal stability and chemical resistance of gallium oxide.
[0078] Pulsed-laser deposition disclosed in NPLs 1 to 3 is not well-suited for forming large-area thin films. As pointed out in NPL 2, forming large-area palladium cobalt oxide thin films on an industrial scale with pulsed-laser deposition is challenging. However, the method for producing a palladium cobalt oxide thin film according to the present embodiment uses sputtering for the deposition of PdCoO.sub.2 thin films, enabling the easy formation of large-area palladium cobalt oxide thin films and making the films suitable for industrial-scale production.
[0079] Additionally, in comparison to the formation method of palladium cobalt oxide thin films by pulsed-laser deposition disclosed in NPLs 1 to 3, the method for producing a palladium cobalt oxide thin film according to the present embodiment does not require the use of two targets with different compositions, as is necessary for pulsed-laser deposition disclosed in NPLs 1 to 3. Instead, it allows for the formation of palladium cobalt oxide thin films using only a single target. Therefore, the production method according to the embodiment simplifies the production of thin films. Furthermore, when two targets with different compositions are used, it becomes challenging to consistently form palladium cobalt oxide thin films with the same composition or crystal structure, resulting in lower reproducibility in production. However, with the production method according to the present embodiment, palladium cobalt oxide thin films can be produced using only a single target, making it easier to consistently form palladium cobalt oxide thin films with the same composition or crystal structure and thereby increasing reproducibility in production.
[0080] Considering the common properties of bulk single crystals of palladium cobalt oxide, palladium chromium oxide, palladium rhodium oxide, and platinum cobalt oxide as delafossite-type oxides, as well as the common properties among palladium, platinum, chromium, cobalt, and rhodium, it is believed that the characteristics demonstrated in the above example associated with the palladium cobalt oxide thin film, the Schottky electrode having a palladium cobalt oxide thin film, and the method for producing a palladium cobalt oxide thin film are, as a matter of fact, also applicable to delafossite-type oxides other than palladium cobalt oxide, namely, palladium chromium oxide, palladium rhodium oxide, and platinum cobalt oxide.
[0081] As described above, a palladium cobalt oxide thin film, a delafossite-type oxide thin film, a Schottky electrode having a delafossite-type oxide thin film, a method for producing a palladium cobalt oxide thin film, and a method for producing a delafossite-type oxide thin film can be provided.
[0082] It should be noted that the embodiment disclosed in this specification is illustrative, and the embodiment of the present disclosure is not limited thereto. Modifications may be appropriately made within the scope that does not deviate from the object of the present disclosure.
INDUSTRIAL APPLICABILITY
[0083] The present disclosure is applicable to palladium cobalt oxide thin films, delafossite-type oxide thin films, Schottky electrodes having delafossite-type oxide thin films, methods for producing palladium cobalt oxide thin films, and methods for producing delafossite-type oxide thin films.