TWI572731B - Transparent oxide film and method for producing the same - Google Patents

Transparent oxide film and method for producing the same Download PDF

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TWI572731B
TWI572731B TW101106025A TW101106025A TWI572731B TW I572731 B TWI572731 B TW I572731B TW 101106025 A TW101106025 A TW 101106025A TW 101106025 A TW101106025 A TW 101106025A TW I572731 B TWI572731 B TW I572731B
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oxide film
transparent oxide
film
sputtering
substrate
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TW101106025A
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TW201247915A (en
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Gou Yamaguchi
Shoubin Zhang
Yuichi Kondou
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Mitsubishi Materials Corp
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Description

透明氧化物膜及其製造方法 Transparent oxide film and method of producing the same

本發明關於一種氣體遮蔽性優異的氧化鋅系之透明氧化物膜及其製造方法，其係可利用作為有機發光顯示元件、液晶顯示元件、電致發光顯示元件、電泳型顯示元件、色粉顯示元件等的電子紙或薄膜型太陽能電池等所使用的氣體遮蔽層或薄膜密封層所含的無機膜及由化合物半導體形成的薄膜太陽能電池的透明電極層上之氣體遮蔽層。 The present invention relates to a zinc oxide-based transparent oxide film having excellent gas barrier properties and a method for producing the same, which can be used as an organic light-emitting display element, a liquid crystal display element, an electroluminescence display element, an electrophoretic display element, and a toner display. An inorganic film contained in a gas shielding layer or a film sealing layer used for an electronic paper such as a device or a thin film solar cell, and a gas shielding layer on a transparent electrode layer of a thin film solar cell formed of a compound semiconductor.

在過去，關於液晶顯示元件或電致發光顯示元件、電泳方式顯示元件、色粉顯示元件等的電子紙或薄膜型太陽能電池等所使用的氣體遮蔽層及由化合物半導體形成的薄膜太陽能電池(例如CIGS(Cu-In-Ga-Se)系太陽能電池)之透明電極層上的氣體遮蔽層，已知有藉由濺鍍法製作透明氧化物膜的技術。 In the past, a gas shielding layer used for an electronic paper such as a liquid crystal display element, an electroluminescence display element, an electrophoretic display element, a toner display element, or the like, a thin film solar cell, or the like, and a thin film solar cell formed of a compound semiconductor (for example, A gas shielding layer on a transparent electrode layer of a CIGS (Cu-In-Ga-Se) solar cell is known as a technique for producing a transparent oxide film by a sputtering method.

例如在專利文獻1中提出了一種之方法，其係使用氧化物燒結體作為濺鍍靶，該氧化物燒結體係含有氧化錫與選自Si、Ge、Al所構成之群中之至少1種添加元素，以相對於添加元素與Sn的含量之總和而言15原子%~63原子%的比例含有該添加元素，在結晶相的構成中含有添加元素的金屬相、該添加元素的氧化物相、該添加元素與Sn的複合氧化物相之中的1種以上，該添加元素的氧化物相及該添加元素與Sn的複合氧化物相，並以平均粒徑 50μm以下的大小分散，利用直流脈衝法的濺鍍法，藉此在樹脂薄膜基材的表面形成透明氧化物膜。 For example, Patent Document 1 proposes a method in which an oxide sintered body containing at least one selected from the group consisting of Si, Ge, and Al is used as a sputtering target. The element contains the additive element in a ratio of 15 atom% to 63 atom% with respect to the total of the content of the additive element and Sn, and the metal phase of the added element and the oxide phase of the additive element are contained in the crystal phase. One or more of the additive element and the composite oxide phase of Sn, the oxide phase of the additive element and the composite oxide of the additive element and Sn, and the average particle diameter A size of 50 μm or less is dispersed, and a transparent oxide film is formed on the surface of the resin film substrate by a sputtering method using a direct current pulse method.

以此方法所得到的透明氧化物膜係含有氧化錫與選自Si、Ge、Al所構成之群中之至少1種添加元素的透明氧化物膜，並且該添加元素的含量係相對於添加元素與Sn的總和而言的15原子%~63原子%的比例，且為非晶質膜，且在波長633nm的折射率為1.90以下。 The transparent oxide film obtained by this method contains a transparent oxide film of tin oxide and at least one additive element selected from the group consisting of Si, Ge, and Al, and the content of the added element is relative to the additive element. The ratio of 15 atom% to 63 atom% with respect to the sum of Sn is an amorphous film, and the refractive index at a wavelength of 633 nm is 1.90 or less.

另外，在專利文獻2中提出了一種光透過膜成膜之方法，其係相變化光碟用保護膜所使用的光透過膜，雖然用途相異，然而使用了含有選自Nb2O5、V2O5、B2O3、SiO2、P2O5之1種以上的玻璃形成氧化物：0.01~20重量%、Al2O3或Ga2O3：0.01~20重量%，剩餘部分為選自In2O3、SnO2、ZnO之1種以上的氧化物的濺鍍靶，藉由濺鍍法，使含有選自Nb2O5、V2O5、B2O3、SiO2、P2O5之1種以上的玻璃形成氧化物：0.01~20重量%、Al2O3或Ga2O3：0.01~20重量%，剩餘部分為選自In2O3、SnO2、ZnO之1種以上的氧化物。 Further, Patent Document 2 proposes a method of forming a light-transmitting film, which is a light-transmitting film used for a phase-change optical film protective film, and although it has a different use, it is selected to contain a material selected from Nb 2 O 5 and V. 1 or more glass forming oxides of 2 O 5 , B 2 O 3 , SiO 2 , and P 2 O 5 : 0.01 to 20% by weight, Al 2 O 3 or Ga 2 O 3 : 0.01 to 20% by weight, and the remainder A sputtering target selected from the group consisting of oxides of at least one of In 2 O 3 , SnO 2 , and ZnO is selected from the group consisting of Nb 2 O 5 , V 2 O 5 , B 2 O 3 , and SiO by sputtering. 2 , one or more kinds of glass forming oxides of P 2 O 5 : 0.01 to 20% by weight, Al 2 O 3 or Ga 2 O 3 : 0.01 to 20% by weight, and the remainder is selected from In 2 O 3 , SnO 2 One or more oxides of ZnO.

[先前技術文獻] [Previous Technical Literature] [專利文獻] [Patent Literature]

[專利文獻1]日本特開2007-290916號公報 [Patent Document 1] Japanese Patent Laid-Open Publication No. 2007-290916

[專利文獻2]日本特開2000-119062號公報 [Patent Document 2] Japanese Patent Laid-Open Publication No. 2000-119062

上述以往的技術殘留了以下的課題。 The above conventional techniques have the following problems.

亦即，在上述專利文獻1之技術所記載之靶中，在濺鍍時會產生許多瘤狀物，在裝置的清掃等需要花費工夫，因此希望有一種非氧化錫系而為其他組成系且氣體遮蔽性優異的透明氧化物膜。然而，藉由上述專利文獻2的技術所製作的透明氧化物膜是用在光碟方面，因此折射率高，在利用於上述電子紙或太陽能電池所使用的樹脂薄膜基材上的氣體遮蔽層時，接近樹脂薄膜基材的折射率(例如在波長633nm且折射率n：1.5~1.7)，因此必須降低其折射率。因此考慮使氧化鋅系之透明氧化物膜含有更多SiO2，以降低折射率，而專利文獻2所記載般，若SiO2超過20wt%，則會有添加的成分的SiO2的結晶相析出的不良狀況。若結晶相析出，則氣體遮蔽性(例如水蒸氣遮蔽性)的機能降低，因此無法作為保護膜使用。 In other words, in the target described in the technique of Patent Document 1, many tumors are generated during sputtering, and it takes time and effort to clean the device. Therefore, it is desirable to have a non-tin oxide system and other components. A transparent oxide film excellent in gas shielding properties. However, the transparent oxide film produced by the technique of the above Patent Document 2 is used for an optical disk, and therefore has a high refractive index when used in a gas shielding layer on a resin film substrate used in the above electronic paper or solar cell. The refractive index of the resin film substrate is close to (for example, at a wavelength of 633 nm and the refractive index n is 1.5 to 1.7), so the refractive index thereof must be lowered. Therefore, it is considered that the zinc oxide-based transparent oxide film contains more SiO 2 to lower the refractive index. As described in Patent Document 2, when SiO 2 exceeds 20% by weight, the crystal phase of the added component of SiO 2 precipitates. Bad condition. When the crystal phase is precipitated, the gas barrier property (for example, water vapor shielding property) is lowered, so that it cannot be used as a protective film.

本發明鑑於前述課題而完成，目的為提供一種氧化鋅系之透明氧化物膜，其係使用成膜速度快的濺鍍法，折射率低，且具有良好的氣體遮蔽性；以及其製造方法。 The present invention has been made in view of the above problems, and an object of the invention is to provide a zinc oxide-based transparent oxide film which is a sputtering method having a high film formation rate, has a low refractive index, and has good gas shielding properties, and a method for producing the same.

由於在AZO(Al-Zn-O：Aluminium doped Zinc Oxide：摻鋁的氧化鋅)膜中含有SiO2，則折射率會變低，因此本發明人等欲藉由濺鍍而使ZnO-SiO2-Al2O3膜成膜以作為透明氧化物膜而進行研究。在此研究之中，查明了藉由將濺鍍成膜時的氣體環境或基板的溫度設定在特定的條件 ，由使用特定的組織所構成之濺鍍靶得到透明、低折射率且具有高氣體遮蔽性能的ZnO-SiO2-Al2O3膜。 Since TiO 2 is contained in the AZO (Al-Zn-O: Aluminium doped Zinc Oxide) film, the refractive index is lowered, so the inventors of the present invention want to make ZnO-SiO 2 by sputtering. The -Al 2 O 3 film was formed into a film to be studied as a transparent oxide film. In this study, it was found that the gas environment or the temperature of the substrate at the time of sputtering film formation is set to a specific condition, and a sputtering target composed of a specific structure is used to obtain a transparent, low refractive index and high. Gas shielding properties of ZnO-SiO 2 -Al 2 O 3 film.

所以，本發明是由上述見解而完成，為了解決前述課題而採用以下的構成。亦即，本發明之透明氧化物膜，其特徵為：具有下述成分組成：相對於金屬成分總量而言含有Al：0.9~20.0at%、Si：25.5~68.0at%，剩餘部分係由Zn及無法避免的雜質所構成，且為非晶質。 Therefore, the present invention has been completed by the above findings, and the following configuration is adopted in order to solve the above problems. That is, the transparent oxide film of the present invention is characterized in that it has a composition of Al: 0.9 to 20.0 at% and Si: 25.5 to 68.0 at% with respect to the total amount of the metal component, and the remainder is Zn and unavoidable impurities are formed and are amorphous.

亦即，在此透明氧化物膜中，由於具有下述成分組成：相對於金屬成分總量而言含有Al：0.9~20.0at%、Si：25.5~68.0at%，剩餘部分係由Zn及無法避免的雜質所構成，且為非晶質，因此在可見光區可得到比以往還低的折射率，同時具有高氣體遮蔽性(例如水蒸氣遮蔽性)。進一步在可見光區可得到95%以上的高透過率，而具有良好的透明性。 That is, the transparent oxide film has a composition of Al: 0.9 to 20.0 at% and Si: 25.5 to 68.0 at% with respect to the total amount of the metal component, and the remainder is Zn and cannot Since the impurities are formed and are amorphous, a refractive index lower than that in the prior art can be obtained in the visible light region, and high gas shielding properties (for example, water vapor shielding properties) can be obtained. Further, in the visible light region, a high transmittance of 95% or more can be obtained, and good transparency is obtained.

此外，將上述Al的含量定為0.9~20.0at%的理由是因為在將濺鍍靶設定成用以得到未達0.9at%的膜的組成的情況，會發生異常放電，無法安定地進行DC濺鍍，將濺鍍靶設定成用以得到超過20.0at%的膜的組成也會發生異常放電，而無法安定地進行DC濺鍍。此外，Al的含量係以12at%以下為較佳。亦即，若Al的含量為12at%以下，則相對而言可維持高Si含量，因此可得到較低的折射率、及較高的氣體遮蔽性。 Further, the reason why the content of Al described above is set to 0.9 to 20.0 at% is because abnormality discharge occurs when the sputtering target is set to have a composition of a film of less than 0.9 at%, and DC cannot be stably performed. In sputtering, the sputtering target is set such that a composition for obtaining a film of more than 20.0 at% also causes abnormal discharge, and DC sputtering cannot be stably performed. Further, the content of Al is preferably 12 at% or less. That is, when the content of Al is 12 at% or less, the high Si content can be relatively maintained, so that a low refractive index and a high gas shielding property can be obtained.

另外，將上述Si的含量定為25.5~68.0at%的理由是因為若未達25.5at%，則無法得到所希望之低折射率及氣 體遮蔽性，在將濺鍍靶設定成用以得到超過68.0at%的膜的組成的情況，Si量變多，而無法進行DC濺鍍。 Further, the reason why the content of Si described above is 25.5 to 68.0 at% is because if it is less than 25.5 at%, the desired low refractive index and gas cannot be obtained. In the case of the bulk shielding property, when the sputtering target is set to have a composition of a film exceeding 68.0 at%, the amount of Si is increased, and DC sputtering cannot be performed.

另外，本發明之透明氧化物膜，其特徵為：在波長750nm的透光率為93%以上。 Further, the transparent oxide film of the present invention is characterized in that the light transmittance at a wavelength of 750 nm is 93% or more.

亦即，與一般能夠以DC濺鍍成膜的氧化物不同，如導電性氧化物般，電子造成長波長側的吸收小，因此能夠製成可藉由DC濺鍍成膜，且可見光長波長的光線不會損失，在可見光全區域具有高透明性的膜。 That is, unlike oxides which are generally capable of being formed by DC sputtering, such as conductive oxides, electrons cause small absorption on the long wavelength side, and thus can be formed by DC sputtering, and visible light has a long wavelength. The light does not lose, and the film has high transparency in the entire visible light region.

另外，本發明之透明氧化物膜，其特徵為：在可見光區的折射率平均值為1.59~1.80，厚度50nm以上且水蒸氣透過率為0.01g/(m2．day)以下。 Further, the transparent oxide film of the present invention is characterized in that the average refractive index in the visible light region is 1.59 to 1.80, the thickness is 50 nm or more, and the water vapor transmission rate is 0.01 g/(m 2 .day) or less.

亦即，在此透明氧化物膜中，在可見光區的折射率平均值為1.59~1.80，厚度50nm以上且水蒸氣透過率為0.01/(m2．day)以下，因此適合作為成膜於電子紙或太陽能電池所可採用的樹脂薄膜基材上的氣體遮蔽層。此外，此處可見光區定為波長380nm~750nm的範圍。 In other words, in the transparent oxide film, the average refractive index in the visible light region is 1.59 to 1.80, the thickness is 50 nm or more, and the water vapor transmission rate is 0.01/(m 2 .day) or less, so that it is suitable for film formation in electrons. A gas shielding layer on a resin film substrate that can be used for paper or solar cells. Further, the visible light region here is set to a wavelength of 380 nm to 750 nm.

本發明之透明氧化物膜之製造方法，其係製造上述發明之透明氧化物膜之方法，其特徵為：使用濺鍍靶，在含有氧的惰性氣體環境中及將基板加熱的狀態之至少一種環境下，通入直流電流以進行濺鍍，該濺鍍靶係由氧化物燒結體所構成，該氧化物燒結體係具有下述成分組成：相對於金屬成分總量而言含有Al：0.3~4.0wt%、Si：6.0~14.5wt%，剩餘部分係由Zn及無法避免的雜質所構成，該燒結體之組織中存在複合氧化物Zn2SiO4與ZnO。 A method for producing a transparent oxide film according to the present invention, which is characterized in that the method of producing a transparent oxide film according to the invention is characterized in that at least one of a sputtering target, an inert gas atmosphere containing oxygen, and a state in which the substrate is heated is used. In the environment, a direct current is applied to perform sputtering, and the sputtering target is composed of an oxide sintered body having a composition of Al: 0.3 to 4.0 with respect to the total amount of the metal component. Wt%, Si: 6.0~14.5wt%, the remainder is composed of Zn and unavoidable impurities, and the composite oxides Zn 2 SiO 4 and ZnO are present in the structure of the sintered body.

亦即，在此透明氧化物膜之製造方法中，係使用在上述氧化物燒結體之組織中存在複合氧化物Zn2SiO4與ZnO的濺鍍靶，因此可進行DC濺鍍，進一步在含有氧的惰性氣體環境中及將基板加熱的狀態之至少一種環境下，通入直流電流以進行濺鍍(DC濺鍍)，因此可使含有許多Si的非晶質透明氧化物膜(ZnO-SiO2-Al2O3膜)成膜。所以，依據本發明之製法，可添加比以往還多的SiO2，降低折射率，同時能夠使非晶質且氣體遮蔽性高的透明氧化物膜以DC濺鍍成膜。 In other words, in the method for producing a transparent oxide film, a sputtering target having a composite oxide of Zn 2 SiO 4 and ZnO in the structure of the oxide sintered body is used, so that DC sputtering can be performed and further contained. In at least one environment in an inert gas atmosphere of oxygen and a state in which the substrate is heated, a direct current is applied to perform sputtering (DC sputtering), so that an amorphous transparent oxide film (ZnO-SiO) containing a large amount of Si can be used. 2 -Al 2 O 3 film) film formation. Therefore, according to the production method of the present invention, more SiO 2 than conventionally can be added, and the refractive index can be lowered, and a transparent oxide film having high amorphous gas shielding properties can be formed by DC sputtering.

此外，將上述Al的含量定為0.3~4.0wt%的理由是因為在未達0.3wt%的情況會發生異常放電而無法進行DC濺鍍，若超過4.0wt%，則所產生的Al2O3與ZnO的複合氧化物ZnAl2O4導致異常放電發生，而無法進行DC濺鍍。 Further, the reason why the content of the above Al is set to 0.3 to 4.0% by weight is because abnormal discharge occurs in the case of less than 0.3% by weight, and DC sputtering cannot be performed. If it exceeds 4.0% by weight, the generated Al 2 O 3 The composite oxide ZnAl 2 O 4 with ZnO causes abnormal discharge to occur, and DC sputtering cannot be performed.

另外，將上述Si的含量定為6.0~14.5wt%的理由是因為在未達6.0wt%的情況無法充分得到降低折射率的效果，若超過14.5wt%，則無法得到充足的導電性，並且發生異常放電，而無法進行DC濺鍍。 In addition, the reason why the content of Si described above is set to 6.0 to 14.5 wt% is because the effect of lowering the refractive index cannot be sufficiently obtained in the case of less than 6.0% by weight, and if it exceeds 14.5 wt%, sufficient conductivity cannot be obtained, and An abnormal discharge occurred and DC sputtering could not be performed.

另外，本發明之透明氧化物膜之成膜方法，其特徵為：前述基板為樹脂薄膜基材，將前述基板之加熱溫度設定在100~200℃的範圍。 Further, in the film forming method of the transparent oxide film of the present invention, the substrate is a resin film substrate, and the heating temperature of the substrate is set to a range of 100 to 200 °C.

亦即，在此透明氧化物膜之製造方法中，將基板的加熱溫度設定在100~200℃的範圍，因此可抑制熱對於成膜的樹脂薄膜基材的影響，同時可得到具有充足的透明性與低折射率的透明氧化物膜以作為電子紙或太陽能電池所可 採用的氣體遮蔽層。 In other words, in the method for producing a transparent oxide film, the heating temperature of the substrate is set in the range of 100 to 200 ° C, so that the influence of heat on the film-forming resin film substrate can be suppressed, and sufficient transparency can be obtained. And low refractive index transparent oxide film for use as electronic paper or solar cells The gas shielding layer used.

此外，將上述基板之加熱溫度設定在100~200℃的範圍的理由是因為若未達100℃，則膜中的Si含量變少，透明性降低，同時折射率變化，若超過200℃，則樹脂薄膜基材會受到損傷。 Further, the reason why the heating temperature of the substrate is set in the range of 100 to 200 ° C is that if the temperature is less than 100 ° C, the Si content in the film is small, the transparency is lowered, and the refractive index is changed. If it exceeds 200 ° C, The resin film substrate is damaged.

另外，本發明之透明氧化物膜之成膜方法，其特徵為：將前述氧相對於氧與惰性氣體之環境氣體全體而言的氣體分壓設定在0.05以上。 Further, the film forming method of the transparent oxide film of the present invention is characterized in that the gas partial pressure of the oxygen with respect to the entire atmosphere of the oxygen and the inert gas is set to 0.05 or more.

亦即，此在透明氧化物膜之製造方法中，將氧相對於氧與惰性氣體之環境氣體全體而言的氣體分壓設定在0.05以上，因此可得到具有充足的透明性與低折射率的透明氧化物膜以作為電子紙或太陽能電池所可採用的氣體遮蔽層。 In other words, in the method for producing a transparent oxide film, the gas partial pressure of oxygen with respect to the entire atmosphere of oxygen and the inert gas is set to 0.05 or more, so that sufficient transparency and low refractive index can be obtained. The transparent oxide film serves as a gas shielding layer which can be used as an electronic paper or a solar cell.

這是因為若使氧的氣體分壓未達0.05，則膜中的Si含量變少，透明性降低，並且折射率發生變化。此外，若氧氣的氣體分壓超過0.2，則濺鍍的成膜速度變慢，生產力降低，因此以定為0.2以下為佳。 This is because if the partial pressure of oxygen gas is less than 0.05, the Si content in the film is reduced, the transparency is lowered, and the refractive index is changed. Further, when the partial pressure of oxygen gas exceeds 0.2, the film formation rate of the sputtering becomes slow, and the productivity is lowered. Therefore, it is preferably 0.2 or less.

以這樣的方式，在本發明中，調整上述基板加熱溫度及上述氧的氣體分壓之至少一者而進行DC濺鍍，可調整膜中Si的含量。 In this manner, in the present invention, at least one of the substrate heating temperature and the oxygen partial pressure of the oxygen is adjusted to perform DC sputtering, and the content of Si in the film can be adjusted.

依據本發明，可發揮出以下的效果。 According to the present invention, the following effects can be exhibited.

亦即，依據本發明所關連之透明氧化物膜，由於具有 下述成分組成：相對於金屬成分總量而言含有Al：0.9~28.5at%、Si：25.5~68.0at%，剩餘部分係由Zn及無法避免的雜質所構成，且為非晶質，因此在可見光區可得到比以往還低的折射率，同時具有高氣體遮蔽性。另外，依據本發明所關連之透明氧化物膜之製造方法，由於使用在上述氧化物燒結體之組織中存在複合氧化物Zn2SiO4與ZnO的濺鍍靶，因此可進行DC濺鍍，在含有氧的惰性氣體環境中及將基板加熱的狀態之至少一種環境下，通入直流電流以進行濺鍍，因此可使非晶質的上述組成之透明氧化物膜(ZnO-SiO2-Al2O3膜)成膜。 That is, the transparent oxide film according to the present invention has a composition of Al: 0.9 to 28.5 at% and Si: 25.5 to 68.0 at% with respect to the total amount of the metal component, and the remainder is Since Zn and unavoidable impurities are formed and are amorphous, a refractive index lower than that in the prior art can be obtained in the visible light region, and high gas shielding properties are obtained. Further, according to the method for producing a transparent oxide film to which the present invention is applied, since a sputtering target having a composite oxide of Zn 2 SiO 4 and ZnO is present in the structure of the oxide sintered body, DC sputtering can be performed. In at least one environment containing an oxygen-containing inert gas and a state in which the substrate is heated, a direct current is applied to perform sputtering, so that an amorphous transparent oxide film of the above composition (ZnO-SiO 2 -Al 2 ) can be used. O 3 film) film formation.

所以，藉由採用本發明之透明氧化物膜作為電子紙或太陽能電池等的氣體遮蔽層，可得到所要求的高透明性、低折射率及高氣體遮蔽性，能夠製作出具有高信賴性以及高視認性的電子紙或轉換效率良好的太陽能電池等。 Therefore, by using the transparent oxide film of the present invention as a gas shielding layer such as an electronic paper or a solar cell, desired high transparency, low refractive index, and high gas shielding property can be obtained, and high reliability can be produced and High-definition electronic paper or solar cells with good conversion efficiency.

以下參照圖1對本發明所關連之透明氧化物膜及其製造方法其中一個實施形態作說明。 Hereinafter, one embodiment of a transparent oxide film and a method for producing the same according to the present invention will be described with reference to FIG.

本實施形態之透明氧化物膜為可利用作為上述用途之氣體遮蔽層的膜，其係具有下述成分組成：相對於金屬成分總量而言含有Al：0.9~20.0at%、Si：25.5~68.0at%，剩餘部分係由Zn及無法避免的雜質所構成，且為非晶質。 The transparent oxide film of the present embodiment is a film which can be used as the gas shielding layer for the above-mentioned use, and has a composition of Al: 0.9 to 20.0 at% and Si: 25.5 to the total amount of the metal component. 68.0 at%, the remainder is composed of Zn and unavoidable impurities, and is amorphous.

另外，此透明氧化物膜在膜厚100nm時的薄片電阻值 為1.0×1014Ω/sq以上。 Further, the sheet resistance of the transparent oxide film at a film thickness of 100 nm was 1.0 × 10 14 Ω/sq or more.

進一步，此透明氧化物膜在可見光區的折射率平均值為1.59~1.80，厚度50nm以上且水蒸氣透過率為0.01g/(m2．day)以下。此外，水蒸氣透過率係根據JIS規格的K7129法，藉由MOCON法所測得的值。 Further, the transparent oxide film has an average refractive index in the visible light region of 1.59 to 1.80, a thickness of 50 nm or more, and a water vapor transmission rate of 0.01 g/(m 2 .day) or less. Further, the water vapor transmission rate is a value measured by the MOCON method in accordance with the K7129 method of JIS standard.

另外，本實施形態之透明氧化物膜之製造方法，係使用濺鍍靶，在含有氧的惰性氣體環境中及將基板加熱的狀態之至少一種環境下，通入直流電流以進行濺鍍(DC濺鍍)，該濺鍍靶係由氧化物燒結體所構成，該氧化物燒結體係具有下述成分組成：相對於金屬成分總量而言含有Al：0.3~4.0wt%、Si：6.0~14.5wt%，剩餘部分係由Zn及無法避免的雜質所構成，在該燒結體的組織中存在複合氧化物Zn2SiO4與ZnO。 Further, in the method for producing a transparent oxide film of the present embodiment, a sputtering target is used, and a direct current is applied to perform sputtering in at least one of an atmosphere containing an inert gas of oxygen and a state in which the substrate is heated. The sputtering target is composed of an oxide sintered body having a composition of Al: 0.3 to 4.0% by weight and Si: 6.0 to 14.5 with respect to the total amount of the metal component. The wt%, the remainder is composed of Zn and unavoidable impurities, and the composite oxides Zn 2 SiO 4 and ZnO are present in the structure of the sintered body.

此時，使用樹脂薄膜基材作為基板，並將基板的加熱溫度設定在100~200℃的範圍。另外，氧相對於氧與惰性氣體之環境氣體全體而言的氣體分壓設定在0.05以上。 At this time, a resin film substrate was used as the substrate, and the heating temperature of the substrate was set to be in the range of 100 to 200 °C. Further, the gas partial pressure of oxygen with respect to the entire atmosphere of the oxygen and the inert gas is set to 0.05 or more.

上述透明薄膜基材可例示丙烯酸樹脂、聚醯胺樹脂、聚醯亞胺樹脂、聚酯樹脂纖維素及該等的共聚合樹脂、合成的透明基板。 The transparent film substrate may, for example, be an acrylic resin, a polyamide resin, a polyimide resin, a polyester resin cellulose, a copolymerized resin or the like, or a synthetic transparent substrate.

詳細的例子可列舉聚酯、聚對苯二甲酸乙二酯(PET)、聚對苯二甲酸丁二酯、聚甲基丙烯酸甲酯(PMMA)、丙烯酸、聚碳酸酯(PC)、聚苯乙烯、聚乙烯醇、聚乙烯等，然而並不在此限。 Specific examples include polyester, polyethylene terephthalate (PET), polybutylene terephthalate, polymethyl methacrylate (PMMA), acrylic acid, polycarbonate (PC), polyphenylene. Ethylene, polyvinyl alcohol, polyethylene, etc., but not limited to this.

此外，上述濺鍍靶的燒結體密度為理論密度的100~ 108%。進一步而言，此濺鍍靶的本體電阻值為1Ω．cm以下。 In addition, the sintered body density of the above sputtering target is 100% of the theoretical density. 108%. Further, the sputtering target has a body resistance value of 1 Ω. Below cm.

將上述燒結體密度定為理論密度比的100~108%的理由是因為在未達100%的情況會發生靶破裂等的問題，若超過108%，則幾乎變成複合氧化物Zn2SiO4的組織，而變得無法藉由DC濺鍍進行放電。 The reason why the density of the sintered body is set to 100 to 108% of the theoretical density ratio is because the problem of target cracking or the like occurs when it is less than 100%, and if it exceeds 108%, it becomes almost the composite oxide Zn 2 SiO 4 . The tissue becomes unable to discharge by DC sputtering.

此處，理論密度比的計算，係使用ZnO為5.61g/cm3、SiO2為2.20g/cm3、Al2O3為3.99g/cm3之值進行計算。 Here, the calculation of the theoretical density ratio was carried out using a value of ZnO of 5.61 g/cm 3 , SiO 2 of 2.20 g/cm 3 , and Al 2 O 3 of 3.99 g/cm 3 .

另外，濺鍍靶的本體電阻值為1Ω．cm以下，因此可安定而良好地進行DC濺鍍。 In addition, the sputtering target has a body resistance of 1 Ω. Below cm, the DC sputtering can be performed stably and satisfactorily.

此製作濺鍍靶之方法係具有，將Al2O3粉末、SiO2粉末、ZnO粉末混合，使其成為Al2O3：0.5~5.0wt%、SiO2：10~22wt%、剩餘部分：由ZnO及無法避免的雜質所構成，而製成混合粉末之步驟；以及在真空中將此混合粉末熱壓延並且燒結之步驟。 The method for producing a sputtering target has a method of mixing Al 2 O 3 powder, SiO 2 powder, and ZnO powder to have Al 2 O 3 : 0.5 to 5.0 wt %, SiO 2 : 10 to 22 wt %, and the remainder: a step of forming a mixed powder composed of ZnO and unavoidable impurities; and a step of thermally calendering and sintering the mixed powder in a vacuum.

若針對上述製法的一個例子作詳細敘述，則例如圖1所示般，首先，秤量純度99.9%以上的Al2O3粉末、SiO2粉末與ZnO粉末，使其成為上述含量範圍，藉由濕式球磨機粉碎、混合，而製作出混合粉末。例如將秤量而得的各粉末與鋯球置入塑膠容器(聚乙烯製罐子)，以球磨機裝置進行濕式混合既定時間，而製成混合粉末。此外，溶劑係使用例如醇。 When an example of the above-described production method is described in detail, for example, as shown in FIG. 1, first, an Al 2 O 3 powder having a purity of 99.9% or more, SiO 2 powder, and ZnO powder are weighed to have the above content range, and wet. The ball mill is pulverized and mixed to prepare a mixed powder. For example, each of the weighed powder and the zirconium ball are placed in a plastic container (polyethylene can), and wet-mixed for a predetermined time by a ball mill apparatus to prepare a mixed powder. Further, the solvent is, for example, an alcohol.

接下來，使所得到的混合粉末乾燥後，例如通過孔徑250μm的篩網而造粒，進一步真空乾燥後，例如以1200℃ 、200kgf/cm2的壓力在真空中熱壓延5小時，而製成燒結體。此外，熱壓延溫度係以1100~1250℃的範圍為佳，壓力係以150~350kgf/cm2的範圍為佳。 Next, the obtained mixed powder is dried, and then granulated by, for example, a sieve having a pore size of 250 μm, and further dried under vacuum, for example, at a pressure of 1200 ° C and a pressure of 200 kgf/cm 2 for 5 hours in a vacuum. Form a sintered body. Further, the hot rolling temperature is preferably in the range of 1100 to 1250 ° C, and the pressure is preferably in the range of 150 to 350 kgf / cm 2 .

以這種方式熱壓延而得的燒結體，通常使用放電加工、切削或研磨加工來進行機械加工而成為指定形狀的靶，並以In作為焊料將加工後的靶焊接於由Cu或SUS(不銹鋼)或其他金屬(例如Mo)所構成之靶座(Backing plate)，然後供給至濺鍍。 The sintered body obtained by hot rolling in this manner is usually machined by electric discharge machining, cutting or polishing to obtain a target of a predetermined shape, and the processed target is welded to Cu or SUS by using In as a solder. A stainless steel or a metal (such as Mo) is used as a backing plate and then supplied to the sputtering.

此外，關於其他製造方法，亦可藉由上述製造方法的濕式球磨機，以純水作為溶劑，使用內部容積300L的球磨裝置磨碎、混合，然後，將藉由噴霧乾燥法進行乾燥造粒而得的物體，進一步以乾式球磨機磨碎，將此磨碎粉末，與上述同樣的方式進行熱壓延之方法。此外亦可省略上述藉由乾式球磨機進行的磨碎步驟。 Further, other production methods may be carried out by a wet ball mill of the above-described production method, using pure water as a solvent, grinding and mixing using a ball mill having an internal volume of 300 L, and then drying and granulating by a spray drying method. The obtained object was further ground by a dry ball mill, and the ground powder was subjected to hot rolling in the same manner as above. Furthermore, the above-mentioned grinding step by a dry ball mill can also be omitted.

為了使用此濺鍍靶進行DC濺鍍以得到本實施形態的透明氧化物膜，將上述濺鍍靶設置於磁控濺鍍裝置，在既定的輸入電力、所到達的真空度、以及濺鍍壓力下，並將濺鍍氣體分壓設定在O2/(Ar+O2)為0.05~0.2的範圍、基板加熱定為100℃至200℃，在此條件下成膜於樹脂薄膜基材上。 In order to obtain the transparent oxide film of the present embodiment by DC sputtering using the sputtering target, the sputtering target is placed in a magnetron sputtering apparatus at a predetermined input power, the degree of vacuum reached, and the sputtering pressure. Next, the partial pressure of the sputtering gas was set to a range of 0.05 to 0.2 in the range of O 2 /(Ar + O 2 ), and the substrate was heated to 100 ° C to 200 ° C under the conditions to form a film on the resin film substrate.

以這樣的方式得到的本實施形態的透明氧化物膜，由於具有下述之成分組成：相對於金屬成分總量而言含有Al：0.9~20.0at%、Si：25.5~68.0at%，剩餘部分係由Zn及無法避免的雜質所構成，且為非晶質，因此在可見光區 可得到比以往還低的折射率，同時具有高氣體遮蔽性(例如水蒸氣遮蔽性)。尤其在可見光區的折射率平均值為1.59~1.80，並藉由將厚度定為50nm以上且水蒸氣透過率定為0.01g/(m2．day)以下，而適合成膜於電子紙或太陽能電池所可採用的樹脂薄膜基材上以作為氣體遮蔽層。 The transparent oxide film of the present embodiment obtained in this manner has a composition of Al: 0.9 to 20.0 at% and Si: 25.5 to 68.0 at% with respect to the total amount of the metal component, and the remainder It is made of Zn and unavoidable impurities, and is amorphous. Therefore, it has a lower refractive index than the conventional one in the visible light region, and has high gas shielding properties (for example, water vapor shielding property). In particular, the average refractive index in the visible light region is 1.59 to 1.80, and is suitable for film formation on electronic paper or solar energy by setting the thickness to 50 nm or more and the water vapor transmission rate to be 0.01 g/(m 2 .day or less). The resin film substrate which can be used for the battery serves as a gas shielding layer.

另外，此在透明氧化物膜之製造方法中，係使用在上述氧化物燒結體之組織中存在複合氧化物Zn2SiO4與ZnO的濺鍍靶，因此可進行DC濺鍍，進一步在含有氧的惰性氣體環境中及將基板加熱的狀態之至少一種環境下，通入直流電流以進行濺鍍，因此可使含有許多Si的非晶質透明氧化物膜(ZnO-SiO2-Al2O3膜)成膜。所以，依據本發明的製法，可添加比以往還多的SiO2，降低折射率，同時能夠使非晶質且氣體遮蔽性高的透明氧化物膜以DC濺鍍成膜。進一步在可見光區可得到95%以上的高透過率，可得到具有良好的透明性的膜。 Further, in the method for producing a transparent oxide film, a sputtering target having a composite oxide of Zn 2 SiO 4 and ZnO in the structure of the oxide sintered body is used, so that DC sputtering can be performed, and oxygen is further contained. In at least one of an inert gas atmosphere and a state in which the substrate is heated, a direct current is applied to perform sputtering, so that an amorphous transparent oxide film containing a large amount of Si (ZnO-SiO 2 -Al 2 O 3 ) can be used. Film) film formation. Therefore, according to the production method of the present invention, more SiO 2 than conventionally can be added, and the refractive index can be lowered, and a transparent oxide film having high amorphous gas shielding properties can be formed by DC sputtering. Further, a high transmittance of 95% or more can be obtained in the visible light region, and a film having good transparency can be obtained.

另外，由於將基板的加熱溫度設定在100~200℃的範圍，因此可抑制熱對於成膜的樹脂薄膜基材產生的影響，同時可得到具有充足的透明性與低折射率的透明氧化物膜以作為電子紙或太陽能電池所能夠採用的氣體遮蔽層。 In addition, since the heating temperature of the substrate is set in the range of 100 to 200 ° C, the influence of heat on the film-forming resin film substrate can be suppressed, and a transparent oxide film having sufficient transparency and low refractive index can be obtained. It is used as a gas shielding layer that can be used as an electronic paper or a solar cell.

進一步，將氧相對於氧與惰性氣體之環境氣體全體而言的氣體分壓設定在0.05以上，因此可得到具有充足的透明性與低折射率的透明氧化物膜以作為電子紙或太陽能電池所能夠採用的氣體遮蔽層。 Further, by setting the gas partial pressure of oxygen to the entire atmosphere of the oxygen and the inert gas to 0.05 or more, a transparent oxide film having sufficient transparency and a low refractive index can be obtained as an electronic paper or a solar cell. A gas shielding layer that can be used.

[實施例] [Examples]

基於上述本實施形態，對所製作出的透明氧化物膜之實施例進行評估，於以下參照圖2至圖8對於所得到的結果作說明。 Based on the above-described embodiment, an example of the produced transparent oxide film was evaluated, and the results obtained will be described below with reference to FIGS. 2 to 8.

本發明之實施例的製造係藉由以下條件進行。 The fabrication of the examples of the present invention was carried out under the following conditions.

首先，秤量Al2O3粉末、SiO2粉末與ZnO粉末使其成為表1所示的組成比例，將所得到的粉末與其4倍量(重量比)的鋯球(直徑5mm的球與直徑10mm的球各一半)置入10L塑膠容器(聚乙烯製罐子)，以球磨機裝置進行濕式混合48小時，而製成混合粉末。此外，溶劑採用例如醇類。 First, the Al 2 O 3 powder, the SiO 2 powder, and the ZnO powder were weighed to have a composition ratio shown in Table 1, and the obtained powder was mixed with a zirconium ball of 4 times (weight ratio) (ball of 5 mm in diameter and diameter of 10 mm). Each of the balls was placed in a 10 L plastic container (polyethylene can) and wet-mixed for 48 hours in a ball mill apparatus to prepare a mixed powder. Further, the solvent is, for example, an alcohol.

接下來使所得到的混合粉末乾燥後，例如通過孔徑250μm的篩網而造粒，進一步真空乾燥後，在1200℃下、200kgf/cm2的壓力進行真空熱壓延5小時，而製成燒結體。 Next, the obtained mixed powder is dried, and then granulated by, for example, a sieve having a pore size of 250 μm, further dried under vacuum, and then vacuum-rolled at 1200 ° C under a pressure of 200 kgf/cm 2 for 5 hours to form a sintered body. body.

將以這樣的方式熱壓延而得的燒結體機械加工成指定形狀的靶(直徑125mm，厚度10mm)，將加工後的靶焊接於由無氧銅所構成的靶座，而製作出本實施例1~16的濺鍍靶。 The sintered body obtained by hot rolling in this manner is machined into a target of a predetermined shape (diameter: 125 mm, thickness: 10 mm), and the processed target is welded to a target block made of oxygen-free copper to prepare the present embodiment. Sputter targets of Examples 1-16.

進一步將這些濺鍍靶設置於磁控濺鍍裝置，條件設定為電源：DC、輸入電力：500W、所到達的真空度：1×10-4Pa、濺鍍氣體分壓(氧相對於氧與惰性氣體之環境氣體全體而言的氣體分壓：O2/(Ar+O2)為0.05以上，濺鍍壓力：0.67Pa、基板加熱溫度100℃至200℃，而嘗試在折 射率及透過率測定用的玻璃基板(Corning公司，1737#長：20×寬：20，厚：0.7mm)上形成膜厚150nm的透明膜，另外，在水蒸氣透過測定用的PET薄膜(長：100mm×寬：100mm，厚：120μm)形成厚50nm的透明膜。 Further, these sputtering targets are set in a magnetron sputtering device, and the conditions are set as a power source: DC, input power: 500 W, degree of vacuum reached: 1 × 10 -4 Pa, sputtering gas partial pressure (oxygen vs. oxygen and Gas partial pressure of the inert gas atmosphere: O 2 /(Ar+O 2 ) is 0.05 or more, sputtering pressure: 0.67Pa, substrate heating temperature 100°C to 200°C, and attempting at refractive index and transmittance A transparent film having a thickness of 150 nm was formed on a glass substrate for measurement (Corning, 1737#length: 20 × width: 20, thickness: 0.7 mm), and a PET film for water vapor transmission measurement (length: 100 mm × width) : 100 mm, thickness: 120 μm) A transparent film having a thickness of 50 nm was formed.

另外，作為密著性測試用，嘗試在聚醯亞胺薄膜(長：100mm×寬：100mm，厚：120μm)形成厚50nm的透明膜。 Further, as a tackiness test, a transparent film having a thickness of 50 nm was formed on a polyimide film (length: 100 mm × width: 100 mm, thickness: 120 μm).

此外，關於比較例的透明氧化物膜，在表1所示的條件之中將基板的加熱溫度定為在100~200℃的範圍外(比較例1、2)；以及將濺鍍靶的Si含量定為未達6.08wt%(比較例3、4)，並以與上述實施例同樣的方式製作出膜。進一步，關於以往例，將濺鍍靶的Si含量定為未達6.08wt%，並且以與上述實施例同樣的方式製作出藉由RF濺鍍成膜的膜。 Further, regarding the transparent oxide film of the comparative example, among the conditions shown in Table 1, the heating temperature of the substrate was set to be outside the range of 100 to 200 ° C (Comparative Examples 1 and 2); and Si of the sputtering target was used. The content was determined to be less than 6.08 wt% (Comparative Examples 3 and 4), and a film was produced in the same manner as in the above Example. Further, in the conventional example, the Si content of the sputtering target was set to be less than 6.08 wt%, and a film formed by RF sputtering was produced in the same manner as in the above examples.

關於以這種方式製作出的本發明之實施例、比較例及以往例之透明氧化物膜，將藉由ICP發光分析法測定膜組成的結果，各金屬成分相對於全部金屬成分的比值揭示於表1。 With respect to the transparent oxide films of the examples, comparative examples, and conventional examples of the present invention produced in this manner, the film composition was measured by ICP emission spectrometry, and the ratio of each metal component to the total metal component was revealed. Table 1.

另外，對本發明之實施例及比較例之透明氧化物膜進行X射線繞射(XRD)的分析，將針對結晶峰的有無調查的結果揭示於表1。此外，代表性地將實施例3、5、6、11及比較例4的XRD分析結果的圖形分別表示於圖2~圖6。 Further, the transparent oxide film of the examples and comparative examples of the present invention was analyzed by X-ray diffraction (XRD), and the results of investigation on the presence or absence of the crystallization peak are shown in Table 1. Further, the graphs of the XRD analysis results of Examples 3, 5, 6, and 11 and Comparative Example 4 are representatively shown in FIGS. 2 to 6 , respectively.

另外，所得到的各透明氧化物膜之折射率係藉由分光橢圓偏光計(HORIBA Jobin Yvon公司製UVISEL NIA AGMS)，透過率係藉由分光光度計(日本分光公司製V-550)作測定。將各測定結果揭示於表1。此外，代表性地將實施例3、5、6、11及比較例4的透過率特性對波長的圖形表示於圖7。另外，將透明氧化物膜的膜厚為50nm、100nm、300nm時在波長750nm的透過率結果揭示於表2。 Further, the refractive index of each of the obtained transparent oxide films was measured by a spectroscopic ellipsometer (UVISEL NIA AGMS, manufactured by HORIBA Jobin Yvon Co., Ltd.), and the transmittance was measured by a spectrophotometer (V-550, manufactured by JASCO Corporation). . The results of each measurement are disclosed in Table 1. Further, the patterns of the transmittance characteristics versus the wavelengths of Examples 3, 5, 6, 11 and Comparative Example 4 are representatively shown in Fig. 7 . Further, the results of the transmittance at a wavelength of 750 nm when the thickness of the transparent oxide film was 50 nm, 100 nm, or 300 nm are shown in Table 2.

進一步使用MOCON法，並使用mocon公司製PERMATRAN-WMODEL3/33，根據JIS規格的K7129法而 測定水蒸氣透過率(水蒸氣遮蔽性)。所測得的各結果如表1所示。此外，代表性地將實施例3、5、6、11及比較例4的折射率特性對波長的的圖形表示於圖8。 Further use the MOCON method and use the PERMATRAN-WMODEL3/33 manufactured by Mocon, according to the K7129 method of the JIS standard. The water vapor transmission rate (water vapor shielding property) was measured. The measured results are shown in Table 1. Further, the patterns of the refractive index characteristics versus wavelengths of Examples 3, 5, 6, 11 and Comparative Example 4 are representatively shown in Fig. 8 .

該等的評估的結果，比較例1、3、4在XRD分析之中觀察到結晶峰，在膜中有結晶析出，水蒸氣透過率亦超過0.01g/(m2．day)。另外，可見光區的折射率超過1.80，同時透過率也低，而未達95%。此外，比較例2的基板加熱溫度高達210℃，因此樹脂薄膜基材發生熱變形，而無法進行評估。進一步而言，在藉由RF濺鍍成膜的以往例的情況，Si的含量低，可見光區的折射率高達2.05，同時透過率亦低達90.6%。 As a result of these evaluations, in Comparative Examples 1, 3, and 4, a crystallization peak was observed in the XRD analysis, and crystals were precipitated in the film, and the water vapor transmission rate was also more than 0.01 g/(m 2 .day). In addition, the refractive index in the visible light region exceeds 1.80, and the transmittance is also low, but less than 95%. Further, since the substrate heating temperature of Comparative Example 2 was as high as 210 ° C, the resin film substrate was thermally deformed and could not be evaluated. Further, in the case of the conventional example in which film formation by RF sputtering, the content of Si is low, the refractive index in the visible light region is as high as 2.05, and the transmittance is also as low as 90.6%.

相對於該等而言，本發明之實施例任一者皆在XRD分析之中並未觀察到結晶峰，而為非晶質的膜，水蒸氣透過率亦在0.01g/(m2．day)以下，而具有高水蒸氣遮蔽性。另外，任一實施例在可見光區的折射率皆為1.80以下，同時透過率亦高達95%以上，可得到低折射率且高透明性的膜。 With respect to these, any of the examples of the present invention did not observe a crystallization peak in the XRD analysis, but an amorphous film, and the water vapor transmission rate was also 0.01 g/(m 2 .day). ), and has high water vapor barrier properties. Further, in any of the examples, the refractive index in the visible light region is 1.80 or less, and the transmittance is also as high as 95% or more, whereby a film having a low refractive index and high transparency can be obtained.

像這樣，本發明實施例之透明氧化物膜任一者為皆電子紙或太陽能電池所能夠採用的氣體遮蔽層，具備適合的膜特性。但是，以實施例16所記載的條件雖然膜的特性優異，然而在濺鍍時氣體環境的O2量多，因此成膜速度變慢。 As described above, any of the transparent oxide films of the examples of the present invention is a gas shielding layer which can be used for both electronic paper and solar cells, and has suitable film properties. However, although the characteristics of the film were excellent under the conditions described in Example 16, the amount of O 2 in the gas atmosphere at the time of sputtering was large, and thus the film formation rate was slow.

<密著性的測定> <Measurement of adhesion>

關於密著性的測定，首先將所得到的薄膜上之透明氧化物膜(實施例1~17、比較例1~7、以往例)以雙面膠帶黏貼在玻璃基板上，在透明氧化物膜上以切刀刻劃成100個棋盤格狀。接下來，在將玻璃紙黏著膠帶貼牢之後，往90°方向急速剝離，並檢查透明氧化物膜剝離的有無。將其結果揭示於表3。將100格之中並未剝離的格子數目以X表示。亦即，有剝離處的情況以X/100表示，沒有剝離處的情況以100/100表示。 For the measurement of the adhesion, first, the transparent oxide film (Examples 1 to 17, Comparative Examples 1 to 7, and the conventional examples) on the obtained film was adhered to a glass substrate with a double-sided tape on a transparent oxide film. It is cut into 100 checkerboard shapes with a cutter. Next, after the cellophane adhesive tape was adhered, it was quickly peeled off in the direction of 90°, and the presence or absence of peeling of the transparent oxide film was examined. The results are disclosed in Table 3. The number of lattices that are not peeled out among 100 cells is represented by X. That is, the case where there is a peeling point is represented by X/100, and the case where there is no peeling is represented by 100/100.

由這些結果可知，在比較例或以往例中發生了剝離，相對於此，本發明之實施例任一者皆剝離並未發生，可得到高密著性。 From these results, it was found that peeling occurred in the comparative example or the conventional example. On the other hand, in any of the examples of the present invention, peeling did not occur, and high adhesion was obtained.

此外，本發明的技術範圍並不受上述實施形態及上述實施例所限定，在不脫離本發明旨趣的範圍，可加入各種 變更。 Further, the technical scope of the present invention is not limited to the above-described embodiments and the above-described embodiments, and various types can be added without departing from the scope of the present invention. change.

例如不只在樹脂薄膜上成膜，相反地，使透明氧化物膜成膜在玻璃上，於其上附加樹脂膜，亦可進一步將樹脂膜與透明氧化物膜一起由玻璃剝離。 For example, not only a film is formed on the resin film, but conversely, a transparent oxide film is formed on the glass, and a resin film is added thereto, and the resin film may be further peeled off from the glass together with the transparent oxide film.

(關於濺鍍靶的參考例) (Reference example for sputtering target)

在本發明中需要藉由DC濺鍍進行成膜，而關於可進行DC濺鍍的濺鍍靶，將檢討結果揭示如下。 In the present invention, it is necessary to form a film by DC sputtering, and the results of the review regarding the sputtering target capable of DC sputtering are disclosed below.

本參考例所關連之濺鍍靶之製造係藉由以下條件來進行。 The manufacture of the sputtering target associated with this reference example was carried out under the following conditions.

首先，以表1所示的各比例秤量Al2O3粉末、SiO2粉末、ZnO粉末，將所得到的粉末與其4倍量(重量比)的鋯球(直徑5mm的球與直徑10mm的球各一半)置入10L塑膠容器(聚乙烯製罐子)，以球磨機裝置濕式混合48小時，而製成混合粉末。此外，溶劑係使用例如醇類。 First, the Al 2 O 3 powder, the SiO 2 powder, and the ZnO powder were weighed in the respective ratios shown in Table 1, and the obtained powder was mixed with a zirconium ball of 4 times by weight (ball of 5 mm in diameter and ball of 10 mm in diameter). Each half was placed in a 10 L plastic container (polyethylene can) and mixed in a ball mill apparatus for 48 hours to prepare a mixed powder. Further, as the solvent, for example, an alcohol is used.

接下來使所得到的混合粉末乾燥後，例如孔徑250μm的篩網而造粒，進一步真空乾燥後，在1200℃下，以200kgf/cm2的壓力真空熱壓延5小時，而製成燒結體。 Next, the obtained mixed powder is dried, and then granulated by, for example, a sieve having a pore size of 250 μm, further dried under vacuum, and then vacuum-rolled at 1200 ° C for 5 hours under a pressure of 200 kgf/cm 2 to obtain a sintered body. .

將以這種方式熱壓延而得的燒結體，機械加工成指定形狀的靶(直徑125mm、厚度10mm)，將加工後的靶焊接於由無氧銅所構成之靶座，而製作出本參考例之濺鍍靶。 The sintered body obtained by hot rolling in this manner is machined into a target of a predetermined shape (diameter: 125 mm, thickness: 10 mm), and the processed target is welded to a target block made of oxygen-free copper to prepare a sintered body. The sputtering target of the reference example.

此外，關於比較參考例1~11，以表2所示的各比例秤量Al2O3粉末、SiO2粉末、ZnO粉末，將所得到的各粉 末混合，以0.6t/cm2壓延，進一步藉由CIP(冷均壓法)以175MPa使其成形，將其在大氣下以1400℃進行燒成，而製作出濺鍍靶。另外，將比較參考例12~14設定在本發明之成分組成的範圍外，以表2所示的各比例秤量，並以與本參考例同樣的條件進行真空熱壓延，而製作出濺鍍靶。 Further, with reference to Comparative Examples 1 to 11, the Al 2 O 3 powder, the SiO 2 powder, and the ZnO powder were weighed in the respective ratios shown in Table 2, and the obtained powders were mixed and rolled at 0.6 t/cm 2 to further borrow It was molded by CIP (cold pressure equalization method) at 175 MPa, and fired at 1400 ° C in the air to prepare a sputtering target. Further, Comparative Reference Examples 12 to 14 were set outside the range of the component composition of the present invention, and weighed at each ratio shown in Table 2, and subjected to vacuum hot rolling under the same conditions as in the present reference example to produce sputtering. target.

進一步將這些濺鍍靶設置於磁控濺鍍裝置，以設定為電源：DC、輸入電力：200W、所到達的真空度：1×10-4Pa、濺鍍氣體：Ar、濺鍍壓力：0.67Pa的條件，加熱至200℃，嘗試在玻璃基板(Corning公司1737#長：20×寬：20，厚：0.7mm)上形成膜厚為300nm的透明膜。 Further, these sputtering targets are set in a magnetron sputtering device to be set as a power source: DC, input power: 200 W, vacuum degree reached: 1 × 10 -4 Pa, sputtering gas: Ar, sputtering pressure: 0.67 The condition of Pa was heated to 200 ° C, and a transparent film having a film thickness of 300 nm was formed on a glass substrate (Corning 1737 #length: 20 × width: 20, thickness: 0.7 mm).

對於以這種方式製作出的本發明之參考例及比較參考例，分別測定以及評估燒結體的密度(理論密度比)、藉由X射線繞射法(XRD)觀察的ZnO(101)及Zn2SiO4(410)的繞射峰的有無、DC濺鍍的可否、本體電阻值、60分鐘的DC濺鍍時的異常放電次數、DC濺鍍後的透明膜的折射率(對於波長380nm、550nm、750nm的光線)。將其結果揭示於表4。 For the reference examples and comparative reference examples of the present invention produced in this manner, the density (theoretical density ratio) of the sintered body and the ZnO (101) and Zn observed by the X-ray diffraction method (XRD) were respectively measured and evaluated. 2 The presence or absence of the diffraction peak of SiO 4 (410), the possibility of DC sputtering, the bulk resistance value, the number of abnormal discharges during DC sputtering for 60 minutes, and the refractive index of the transparent film after DC sputtering (for wavelength 380 nm, 550nm, 750nm light). The results are disclosed in Table 4.

由此結果可知，採用大氣燒成的比較參考例之中，在Al2O3的含量少且不含SiO2的比較參考例1、2的情況，異常放電次數多，無法安定地進行DC濺鍍，在Al2O3的含量達某程度然而不含SiO2的比較參考例3~5的情況，並未得到低折射率。另外，在採用大氣燒成的比較參考例之中，在Al2O3的含量多且不含SiO2的比較參考例6、7的情況，異常放電次數多，無法安定地進行DC濺鍍，在含有Al2O3與SiO2的比較參考例8~11中，異常放電次數多，或靶不具有導電性，而無法進行DC濺鍍。此外，比較參考例1~7任一者的密度皆未達理論密度的100%。 As a result of the comparison, in the comparative reference examples in which the content of Al 2 O 3 is small and the comparative reference examples 1 and 2 in which SiO 2 is not contained, the number of abnormal discharges is large, and DC sputtering cannot be performed stably. In the case of the comparative reference examples 3 to 5 in which the content of Al 2 O 3 was a certain degree but the SiO 2 was not contained, the low refractive index was not obtained. In the comparative reference examples in which the content of Al 2 O 3 is large and the comparative examples 6 and 7 in which SiO 2 is not contained, the number of abnormal discharges is large, and DC sputtering cannot be performed stably. In Comparative Reference Examples 8 to 11 containing Al 2 O 3 and SiO 2 , the number of abnormal discharges was large, or the target did not have conductivity, and DC sputtering could not be performed. Further, the density of any of Comparative Reference Examples 1 to 7 was less than 100% of the theoretical density.

進一步而言，使用熱壓延的比較參考例之中，在SiO2的含量少於本發明範圍的比較參考例12的情況，無法得到低折射率，在SiO2的含量高於本發明範圍的比較參考例13的情況，靶不具有導電性，而無法進行DC濺鍍。另外，在Al2O3的含量高於本發明的範圍的比較參考例14中，異常放電次數多，無法安定地進行DC濺鍍。此外，在比較參考例8、12、14的情況，在XRD之中觀察到ZnO(101)及Zn2SiO4(410)這兩個峰，然而Al或Si的含量在本發明的範圍外，因此發生上述不良狀況。 Further, among the comparative reference examples using the hot calendering, in the case of Comparative Reference Example 12 in which the content of SiO 2 is less than the range of the present invention, a low refractive index cannot be obtained, and the content of SiO 2 is higher than the range of the present invention. In the case of Comparative Reference Example 13, the target was not electrically conductive, and DC sputtering could not be performed. Further, in Comparative Reference Example 14 in which the content of Al 2 O 3 was higher than the range of the present invention, the number of abnormal discharges was large, and DC sputtering could not be performed stably. Further, in the case of comparing Reference Examples 8, 12, and 14, two peaks of ZnO (101) and Zn 2 SiO 4 (410) were observed in XRD, but the content of Al or Si was outside the range of the present invention. Therefore, the above-mentioned adverse conditions occur.

相對於該等而言，本參考例任一者皆在XRD之中觀察到ZnO(101)及Zn2SiO4(410)這兩個峰，異常放電次數非常少，可安定而良好地進行DC濺鍍，關於折射率，任一者皆可得低於到AZO膜的折射率。 With respect to these, in either of the present examples, two peaks of ZnO (101) and Zn 2 SiO 4 (410) were observed in XRD, and the number of abnormal discharges was very small, and DC could be stably and favorably performed. Sputtering, with respect to the refractive index, can be lower than the refractive index to the AZO film.

另外，關於密度，在本參考例的情況，任一者皆在理 論密度的100~108%的範圍內。 In addition, regarding the density, in the case of this reference example, either one is reasonable. On the range of density of 100~108%.

接下來將藉由X射線繞射法(XRD)對於表1所示的參考例3(SiO2=20wt%)進行觀察所得到的結果表示於圖9。在此參考例3中，複合氧化物Zn2SiO4的(410)繞射峰與ZnO的(101)繞射峰任一者皆可觀察到高強度。相對於此，在由與參考例3相同的成分組成於大氣下進行燒成所製作出的比較參考例的情況，如圖10所示般，並未得到ZnO的(101)繞射峰。像這樣為了得到導電性，如本參考例般，複合氧化物Zn2SiO4與ZnO必須共存於組織中。 Next, the results obtained by observing Reference Example 3 (SiO 2 = 20 wt%) shown in Table 1 by X-ray diffraction (XRD) are shown in Fig. 9. In Reference Example 3, high strength was observed in either the (410) diffraction peak of the composite oxide Zn 2 SiO 4 and the (101) diffraction peak of ZnO. On the other hand, in the case of the comparative reference example produced by firing in the same composition as in Reference Example 3, as shown in FIG. 10, the (101) diffraction peak of ZnO was not obtained. In order to obtain conductivity as described above, the composite oxide Zn 2 SiO 4 and ZnO must coexist in the structure as in the present reference example.

圖1係表示本發明所關連之透明氧化物膜及其製造方法其中一個實施形態中，所使用的濺鍍靶之製造步驟之流程圖。 BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a flow chart showing the steps of manufacturing a sputtering target used in one embodiment of a transparent oxide film and a method for producing the same according to the present invention.

圖2係表示在本發明所關連之透明氧化物膜及其製造方法之實施例之中，透明氧化物膜(實施例3)之X射線繞射(XRD)之分析結果之圖形。 Fig. 2 is a graph showing the results of analysis of X-ray diffraction (XRD) of a transparent oxide film (Example 3) in an embodiment of a transparent oxide film and a method for producing the same according to the present invention.

圖3係表示在本發明所關連之透明氧化物膜及其製造方法之實施例之中，透明氧化物膜(實施例5)之X射線繞射之分析結果之圖形。 Fig. 3 is a graph showing the results of analysis of X-ray diffraction of a transparent oxide film (Example 5) in the embodiment of the transparent oxide film and the method for producing the same according to the present invention.

圖4係表示在本發明所關連之透明氧化物膜及其製造方法之實施例之中，透明氧化物膜(實施例6)之X射線繞射之分析結果之圖形。 Fig. 4 is a graph showing the results of analysis of X-ray diffraction of a transparent oxide film (Example 6) in the embodiment of the transparent oxide film and the method for producing the same according to the present invention.

圖5係表示在本發明所關連之透明氧化物膜及其製造方法之實施例之中，透明氧化物膜(實施例11)之X射線繞射之分析結果之圖形。 Fig. 5 is a graph showing the results of analysis of X-ray diffraction of a transparent oxide film (Example 11) in the embodiment of the transparent oxide film and the method for producing the same according to the present invention.

圖6係表示在本發明所關連之透明氧化物膜及其製造方法之比較例之中，透明氧化物膜(比較例4)之X射線繞射之分析結果之圖形。 Fig. 6 is a graph showing the results of analysis of X-ray diffraction of a transparent oxide film (Comparative Example 4) in a comparative example of the transparent oxide film and the method for producing the same according to the present invention.

圖7係表示在本發明所關連之透明氧化物膜及其製造方法之實施例及比較例之中，透過率對於波長之圖形。 Fig. 7 is a graph showing the transmittance versus wavelength in the examples and comparative examples of the transparent oxide film and the method for producing the same according to the present invention.

圖8係表示在本發明所關連之透明氧化物膜及其製造方法之實施例及比較例之中，折射率對於波長之圖形。 Fig. 8 is a graph showing the refractive index versus wavelength in the examples and comparative examples of the transparent oxide film and the method for producing the same according to the present invention.

圖9係表示在參考例之中，濺鍍靶之X射線繞射(XRD)之分析結果之圖形。 Fig. 9 is a graph showing the results of analysis of X-ray diffraction (XRD) of a sputtering target among the reference examples.

圖10係表示在比較參考例之中，濺鍍靶之X射線繞射(XRD)之分析結果之圖形。 Fig. 10 is a graph showing the results of analysis of X-ray diffraction (XRD) of a sputtering target among comparative reference examples.

Claims (6)

一種透明氧化物膜，其特徵為：具有下述成分組成，且為非晶質，水蒸氣透過率為0.01g/(m2．day)以下；相對於金屬成分總量而言含有Al：0.9~20.0at%、Si：25.5~68.0at%，且剩餘部分係由Zn及無法避免的雜質所構成。 A transparent oxide film characterized by having the following composition and being amorphous, having a water vapor transmission rate of 0.01 g/(m 2 .day) or less; and containing Al: 0.9 with respect to the total amount of metal components ~20.0at%, Si: 25.5~68.0at%, and the rest is composed of Zn and unavoidable impurities. 如申請專利範圍第1項之透明氧化物膜，其係在波長750nm的透過率為93%以上。 The transparent oxide film of claim 1 is a transmittance of 93% or more at a wavelength of 750 nm. 如申請專利範圍第1項之透明氧化物膜，其係在可見光區的折射率平均值為1.59~1.80，厚度為50nm以上且水蒸氣透過率為0.01g/(m2．day)以下。 The transparent oxide film according to the first aspect of the invention is characterized in that the average refractive index in the visible light region is 1.59 to 1.80, the thickness is 50 nm or more, and the water vapor transmission rate is 0.01 g/(m 2 .day) or less. 一種透明氧化物膜之製造方法，其係製造如申請專利範圍第1項之透明氧化物膜之方法，其特徵為：使用濺鍍靶，在含有氧的惰性氣體環境中及將基板加熱的狀態之至少一種環境下，通入直流電流以進行濺鍍，該濺鍍靶係由氧化物燒結體所構成，該氧化物燒結體係具有下述成分組成：相對於金屬成分總量而言含有Al：0.3~4.0wt%、Si：6.0~14.5wt%，且剩餘部分係由Zn及無法避免的雜質所構成，並且在該燒結體之組織中存在複合氧化物Zn2SiO4與ZnO。 A method for producing a transparent oxide film, which is a method for producing a transparent oxide film according to claim 1, characterized in that a sputtering target is used in an inert gas atmosphere containing oxygen and a substrate is heated In at least one of the environments, a direct current is applied to perform sputtering, and the sputtering target is composed of an oxide sintered body having the following composition: containing Al with respect to the total amount of the metal component: 0.3 to 4.0 wt%, Si: 6.0 to 14.5 wt%, and the remainder is composed of Zn and unavoidable impurities, and a composite oxide of Zn 2 SiO 4 and ZnO exists in the structure of the sintered body. 如申請專利範圍第4項之透明氧化物膜之製造方 法，其中前述基板為樹脂薄膜基材，且將前述基板之加熱溫度設定在100~200℃的範圍。 For example, the manufacturer of the transparent oxide film of claim 4 In the method, the substrate is a resin film substrate, and the heating temperature of the substrate is set in a range of 100 to 200 °C. 如申請專利範圍第4項之透明氧化物膜之製造方法，其中將前述氧相對於氧與惰性氣體之環境氣體全體而言的氣體分壓設定在0.05以上。 The method for producing a transparent oxide film according to the fourth aspect of the invention, wherein the gas partial pressure of the oxygen relative to the entire atmosphere of the oxygen and the inert gas is set to 0.05 or more.
TW101106025A 2011-02-25 2012-02-23 Transparent oxide film and method for producing the same TWI572731B (en)

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