TWI696581B - Nitrogen oxide film and capacitor - Google Patents

Nitrogen oxide film and capacitor Download PDF

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TWI696581B
TWI696581B TW107111242A TW107111242A TWI696581B TW I696581 B TWI696581 B TW I696581B TW 107111242 A TW107111242 A TW 107111242A TW 107111242 A TW107111242 A TW 107111242A TW I696581 B TWI696581 B TW I696581B
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thin film
dielectric thin
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TW201841825A (en
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芝原豪
永峰佑起
田中美知
山久美子
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日商Ｔｄｋ股份有限公司
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Abstract

本發明提供一種介電特性優異的介電質薄膜及電容元件。此介電質薄膜其特徵在於，此介電質薄膜具有由以組成式Aa Bb Oo Nn （a＋b＋o＋n＝5）表示的氮氧化物構成的主組成，所述A為Sr、Ba、Ca、La、Ce、Pr、Nd、Na的任意一種以上，所述B為Ta、Nb、Ti、W的任意一種以上，構成此介電質薄膜的結晶粒子為未向某特定的晶面方向取向的多晶，此介電質薄膜所包含的結晶粒子的晶粒的尺寸為100nm以下。The invention provides a dielectric thin film and a capacitor element with excellent dielectric characteristics. This dielectric thin film is characterized in that the dielectric thin film has a main composition composed of a nitrogen oxide represented by a composition formula A a B b O o N n (a+b+o+n=5), where A is Sr, Ba, Ca, La, Ce, Pr, Nd, or Na, and B is any one or more of Ta, Nb, Ti, and W. The crystal particles constituting the dielectric thin film are not oriented in a specific crystal plane For oriented polycrystals, the size of crystal grains of the crystalline particles contained in this dielectric thin film is 100 nm or less.

Description

氮氧化物薄膜與電容元件Nitrogen oxide film and capacitor

本發明涉及具有由氮氧化物構成的主組成的介電質薄膜及包含其的電容元件。The present invention relates to a dielectric thin film mainly composed of nitrogen oxide and a capacitor element including the same.

近年來，隨著數碼設備的小型化、高性能化，尋求使用了高性能的介電質薄膜的電容元件。In recent years, with the miniaturization and high performance of digital devices, capacitor elements using high-performance dielectric thin films have been sought.

一直以來，作為介電質薄膜，廣泛使用著使用了金屬氧化物材料的薄膜。但是，由金屬氧化物材料帶來的介電質薄膜的特性提高遇到了極限，正在尋求具有更高特性的新的材料。作為新的材料的候補之一，可以舉出將鈣鈦礦晶體結構的氧八面體中的氧原子的一部分置換成氮原子的金屬氮氧化物材料。但是，難以得到具有金屬氮氧化物材料的介電質薄膜。Conventionally, thin films using metal oxide materials have been widely used as dielectric thin films. However, the improvement of the characteristics of dielectric thin films brought about by metal oxide materials has encountered a limit, and new materials with higher characteristics are being sought. As one of the candidates for the new material, a metal oxynitride material in which a part of oxygen atoms in the oxygen octahedral of the perovskite crystal structure is replaced with nitrogen atoms can be mentioned. However, it is difficult to obtain a dielectric thin film having a metal oxynitride material.

例如，專利文獻1及專利文獻2中記載有一種製作鈣鈦礦型氮氧化物ABO2 N的粉末的方法。但是，在專利文獻1及專利文獻2中，並未公開任何關於得到使用了鈣鈦礦型氮氧化物ABO2 N的薄膜。For example, Patent Document 1 and Patent Document 2 describe a method of preparing a powder of perovskite-type nitrogen oxide ABO 2 N. However, Patent Document 1 and Patent Document 2 do not disclose anything about obtaining a thin film using perovskite-type oxynitride ABO 2 N.

另外，非專利文獻1及非專利文獻2中記載有製作由鈣鈦礦型氮氧化物ABO2 N構成的薄膜的內容。但是，非專利文獻1及非專利文獻2中得到的薄膜為磊晶膜。In addition, Non-Patent Document 1 and Non-Patent Document 2 describe the production of a thin film composed of perovskite-type oxynitride ABO 2 N. However, the thin films obtained in Non-Patent Document 1 and Non-Patent Document 2 are epitaxial films.

磊晶膜存在在其製造時花費大量時間的缺點。非專利文獻1中的內容有記載製造厚度20nm以下的磊晶膜時花費530小時以下如此長的時間。 現有技術文獻 專利文獻The epitaxial film has a disadvantage that it takes a lot of time to manufacture it. Non-Patent Document 1 describes that it takes 530 hours or less to produce an epitaxial film with a thickness of 20 nm or less. Prior Art Literature Patent Literature

專利文獻1：日本特開昭61-122108號公報 專利文獻2：日本特開2013-001625號公報 非專利文獻Patent Document 1: Japanese Patent Laid-Open No. 61-122108 Patent Document 2: Japanese Patent Laid-Open No. 2013-001625 Non-Patent Document

非專利文獻1：Scientific Reports 4. DOI: 10.1038/srep04987 非專利文獻2：KAST 平成25年度研究概要 32-33頁Non-Patent Literature 1: Scientific Reports 4. DOI: 10.1038/srep04987 Non-Patent Literature 2: KAST Heisei 25 Annual Research Summary 32-33 pages

發明所要解決的課題Problems to be solved by the invention

本發明鑒於這樣的實際狀況，其目的在於提供一種製造效率高、介電特性優異之具有由氮氧化物構成的主組成的介電質薄膜及包含其的電容元件。 用於解決課題的技術手段In view of such an actual situation, the present invention aims to provide a dielectric thin film having a main composition composed of nitrogen oxide and a capacitive element including the same, which has high manufacturing efficiency and excellent dielectric characteristics. Technical means for solving problems

本發明所涉及的介電質薄膜其特徵在於此介電質薄膜具有由組成式Aa Bb Oo Nn （a＋b＋o＋n＝5）表示的氮氧化物構成的主組成， A為Sr、Ba、Ca、La、Ce、Pr、Nd、Na的任意一種以上， B為Ta、Nb、Ti、W的任意一種以上， 構成此介電質薄膜的結晶粒子為未向某特定的晶面方向取向的多晶，此介電質薄膜所包含的結晶粒子的晶粒的尺寸為100nm以下。The dielectric thin film according to the present invention is characterized in that the dielectric thin film has a main composition composed of a nitrogen oxide represented by the composition formula A a B b O o N n (a+b+o+n=5), where A is Sr, Ba, Ca, La, Ce, Pr, Nd, or Na, B is any one of Ta, Nb, Ti, and W. The crystal particles constituting the dielectric thin film are not oriented in a specific crystal plane direction Polycrystalline, the crystal grains included in this dielectric thin film have a crystal grain size of 100 nm or less.

本發明所涉及的介電質薄膜藉由藉由具有上述的特徵，能夠提高介電特性。The dielectric thin film according to the present invention can improve the dielectric characteristics by having the aforementioned characteristics.

對於介電質薄膜，基於藉由面外（Out-of-Plane）法進行X射線繞射測定得到的結果算出的晶粒的尺寸為基於藉由面內（In-Plane）法進行X射線繞射測定得到的結果算出的晶粒的尺寸的1.5倍以上為佳。For the dielectric thin film, the size of the crystal grain calculated based on the result of X-ray diffraction measurement by the out-of-plane method is based on the X-ray winding by the in-plane (In-Plane) method. It is preferable that the size of the crystal grain calculated from the results obtained by the radiographic measurement is 1.5 times or more.

A為Sr， B為Ta及/或Nb，所述n大於0且小於1為佳。A is Sr, B is Ta and/or Nb, preferably n is greater than 0 and less than 1.

本發明所涉及的電容元件具有此介電質薄膜。The capacitor element according to the present invention has this dielectric film.

以下，說明本發明的實施方式。Hereinafter, embodiments of the present invention will be described.

圖1中表示本實施方式的薄膜電容器（電容元件）的示意圖。圖1所示的薄膜電容器1在基板11上依序形成下部電極12、介電質薄膜13，並在介電質薄膜13上具備上部電極14。FIG. 1 shows a schematic diagram of a film capacitor (capacitive element) of this embodiment. In the thin film capacitor 1 shown in FIG. 1, a lower electrode 12 and a dielectric thin film 13 are sequentially formed on a substrate 11, and an upper electrode 14 is provided on the dielectric thin film 13.

基板11的材質沒有特別限制，但使用Si單晶基板作為基板11時取得容易性及成本性優異。在重視撓性的情況下，也能夠使用Ni箔作為基板。The material of the substrate 11 is not particularly limited, but when a Si single crystal substrate is used as the substrate 11, it is easy to obtain and cost-effective. When flexibility is important, Ni foil can also be used as a substrate.

下部電極12及上部電極14的材質沒有特別限制，只要作為電極發揮作用即可。例如，可以舉出Pt、Ag、Ni等。下部電極12的厚度以0.01～10μm為佳。上部電極14的厚度以0.01～10μm為佳。The materials of the lower electrode 12 and the upper electrode 14 are not particularly limited, as long as they function as electrodes. For example, Pt, Ag, Ni, etc. may be mentioned. The thickness of the lower electrode 12 is preferably 0.01 to 10 μm. The thickness of the upper electrode 14 is preferably 0.01 to 10 μm.

介電質薄膜13具有以組成式Aa Bb Oo Nn （a＋b＋o＋n＝5）表示的氮氧化物構成的主組成。The dielectric thin film 13 has a main composition composed of nitrogen oxide represented by the composition formula A a B b O o N n (a+b+o+n=5).

A為選自Sr、Ba、Ca、La、Ce、Pr、Nd、Na中的一種以上的元素。A為選自Sr、Ba、La、Nd中的一種以上的元素為佳。A為Sr更佳。藉由使用上述元素作為A，可以得到較高的電容。B為選自Ta、Nb、Ti、W中的一種以上的元素。B為選自Ta、Nb中的一種以上的元素為佳。B為Ta更佳。藉由使用上述元素作為B，可以得到異相較少的介電質薄膜13。A is one or more elements selected from Sr, Ba, Ca, La, Ce, Pr, Nd, and Na. A is preferably one or more elements selected from Sr, Ba, La, and Nd. A is better for Sr. By using the above elements as A, a higher capacitance can be obtained. B is one or more elements selected from Ta, Nb, Ti, and W. B is preferably one or more elements selected from Ta and Nb. B is better for Ta. By using the above elements as B, a dielectric thin film 13 with less out-of-phase can be obtained.

另外，組成式Aa Bb Oo Nn 中，a＜1為佳。另外，a/b＞1為佳，a/b≧1.05更佳。另外，1＞n＞0為佳，1＞n≧0.3更佳，1＞n≧0.5特佳。藉由將a、b及n設為上述的範圍，可以得到良好的介電特性。In the composition formula A a B b O o N n , a<1 is preferred. In addition, a/b>1 is preferable, and a/b≧1.05 is more preferable. In addition, 1>n>0 is preferred, 1>n≧0.3 is more preferred, and 1>n≧0.5 is particularly preferred. By setting a, b, and n to the above range, good dielectric characteristics can be obtained.

構成介電質薄膜13的結晶粒子X為未向某特定的晶面方向取向的多晶。The crystal particles X constituting the dielectric thin film 13 are polycrystals that are not oriented in a certain crystal plane direction.

如圖2所示，上述結晶粒子X包含多個縱長的晶粒Y。晶粒Y是在上述結晶粒子X內，由同一晶面構成的結晶的最小單元。因此，晶粒Y彼此的連接部的晶格不連續，在其連接部並不存在異相或晶界，作為組成及結晶性連續，該連續的晶粒的集合體為結晶粒子X。一個結晶粒子X中，多個晶粒Y的晶面朝向同一方向。位於結晶粒子X彼此的連接部之相當於晶界面的界面，能夠利用透射電子顯微鏡（TEM）進行觀察。As shown in FIG. 2, the crystal particles X include a plurality of vertically long crystal grains Y. The crystal grain Y is the smallest unit of the crystal composed of the same crystal plane in the crystal particle X. Therefore, the lattice of the connection part between the crystal grains Y is discontinuous, and there is no heterophase or grain boundary at the connection part. The composition and crystallinity are continuous, and the aggregate of the continuous crystal grains is the crystal particle X. In one crystal particle X, the crystal planes of a plurality of crystal grains Y face the same direction. The interface corresponding to the crystal interface at the connection portion of the crystal particles X can be observed with a transmission electron microscope (TEM).

本實施方式中，上述結晶粒子X所包含的晶粒Y的尺寸為100nm以下。藉由將晶粒Y的尺寸設為100nm以下，能夠提高介電特性。晶粒Y的尺寸基於如圖4所示的TEM圖像進行測定。In this embodiment, the size of the crystal grains Y included in the crystal particles X is 100 nm or less. By setting the size of the crystal grain Y to 100 nm or less, the dielectric characteristics can be improved. The size of the crystal grain Y is measured based on the TEM image shown in FIG. 4.

一般而言，已知藉由縮小構成介電質薄膜的結晶粒子所包含的晶粒的尺寸，能夠較小地抑制介電常數相對於頻率的變化率。另一方面，還已知如果縮小晶粒的尺寸，則得到的相對介電常數也變小。特別是已知用作高電容的介電質的鈦酸鋇，藉由縮小晶粒的尺寸會難以得到密排六方晶格中的較高的軸比（c/a比），在晶粒的尺寸為100nm以下時，相對介電常數極端地降低。即使晶粒尺寸為100nm以下，也可以得到較高的相對介電常數，則成為介電常數相對於頻率的變化也較小的理想的介電質，但一直以來沒有報告這樣的介電質。本實施方式中，即使將構成介電質薄膜的結晶粒子設為未向某特定的晶面方向取向的多晶，且將結晶粒子所包含的晶粒的尺寸設為100nm以下，也較小地抑制相對介電常數相對於頻率的變化率，並且能夠提高相對介電常數。In general, it is known that by reducing the size of crystal grains included in the crystal particles constituting the dielectric thin film, the rate of change of the dielectric constant with respect to frequency can be suppressed to a small extent. On the other hand, it is also known that if the size of crystal grains is reduced, the relative dielectric constant obtained also becomes smaller. In particular, it is known that barium titanate, which is used as a high-capacitance dielectric, is difficult to obtain a high axial ratio (c/a ratio) in a closely packed hexagonal lattice by reducing the size of the crystal grain. When the size is 100 nm or less, the relative dielectric constant decreases extremely. Even if the crystal grain size is 100 nm or less, a high relative dielectric constant can be obtained, and it becomes an ideal dielectric with a small change in dielectric constant with respect to frequency, but such a dielectric has not been reported so far. In this embodiment, even if the crystal particles constituting the dielectric thin film are polycrystals that are not oriented in a certain crystal plane direction, and the size of crystal grains included in the crystal particles is set to 100 nm or less, it is small The rate of change of the relative dielectric constant with respect to frequency is suppressed, and the relative dielectric constant can be increased.

另外，對於介電質薄膜13，基於藉由面外法進行X射線繞射測定得到的結果算出的晶粒的尺寸較佳為基於藉由面內法進行X射線繞射測定得到的結果算出的晶粒的尺寸的1.5倍以上，1.8倍以上更佳，2.5倍以上特佳。透過將藉由面外法得到的晶粒的尺寸與藉由面內法得到的晶粒的尺寸的比率設為上述範圍，能夠提高介電特性。In addition, for the dielectric thin film 13, the size of crystal grains calculated based on the results of X-ray diffraction measurement by the out-of-plane method is preferably calculated based on the results of X-ray diffraction measurement by the in-plane method. The size of the crystal grains is more than 1.5 times, more preferably 1.8 times or more, and particularly preferably 2.5 times or more. By setting the ratio of the size of the crystal grain obtained by the out-of-plane method to the size of the crystal grain obtained by the in-plane method to the above range, the dielectric characteristics can be improved.

此外，在面外法中，如圖3（a）所示，從介電質薄膜的表面以5～90°的角度範圍照射入射X射線R，根據其繞射X射線R’評價晶粒的尺寸。由此，能夠測定晶粒在介電質薄膜的厚度方向（縱向）的大小。In addition, in the out-of-plane method, as shown in FIG. 3(a), incident X-rays R are irradiated from the surface of the dielectric thin film at an angle ranging from 5 to 90°, and the crystal grains are evaluated based on the diffraction X-rays R′ size. Thus, the size of the crystal grains in the thickness direction (longitudinal direction) of the dielectric thin film can be measured.

另外，如圖3（b）所示，面內法是從介電質薄膜的側面，將入射角固定成全反射臨界角度附近（0.2～0.5°）的較小的角度，並照射入射X射線R，根據繞射X射線R’評價晶粒的尺寸。由此，能夠測定晶粒的橫向的大小。In addition, as shown in FIG. 3(b), the in-plane method fixes the incident angle from the side of the dielectric thin film to a small angle near the critical angle of total reflection (0.2 to 0.5°), and irradiates the incident X-ray R , Evaluate the size of the crystal grains based on the diffraction X-ray R'. This makes it possible to measure the lateral size of the crystal grains.

介電質薄膜13的厚度沒有特別限制，但以10nm～2μm為佳，以10nm～1μm更佳。The thickness of the dielectric thin film 13 is not particularly limited, but it is preferably 10 nm to 2 μm, more preferably 10 nm to 1 μm.

介電質薄膜13的相對介電常數ε沒有特別限定，但以1800以上為佳，以2500以上更佳，以2700以上特佳。藉由將相對介電常數ε設為上述範圍，可以得到介電特性優異的介電質薄膜。 此外，相對介電常數ε能夠藉由在電壓1Vrms/μm、頻率20Hz～10kHz的條件下進行測定。The relative dielectric constant ε of the dielectric thin film 13 is not particularly limited, but it is preferably 1800 or more, more preferably 2500 or more, and particularly preferably 2700 or more. By setting the relative dielectric constant ε to the above range, a dielectric thin film having excellent dielectric characteristics can be obtained. In addition, the relative dielectric constant ε can be measured under the conditions of a voltage of 1 Vrms/μm and a frequency of 20 Hz to 10 kHz.

介電質薄膜13的相對介電常數變化率Δε以低於±20%為佳，以±10%以內更佳。藉由將相對介電常數變化率Δε設為上述範圍，可以得到介電特性優異的介電質薄膜。 此外，相對介電常數變化率Δε能夠藉由以頻率20Hz及10kHz測得的相對介電常數的差，除以以頻率20Hz測得的相對介電常數而算出。The relative dielectric constant change rate Δε of the dielectric thin film 13 is preferably less than ±20%, and more preferably within ±10%. By setting the relative dielectric constant change rate Δε within the above range, a dielectric thin film having excellent dielectric characteristics can be obtained. In addition, the relative permittivity change rate Δε can be calculated by dividing the difference in relative permittivity measured at frequencies 20 Hz and 10 kHz by the relative permittivity measured at frequency 20 Hz.

薄膜電容器1的製造方法 接著，說明薄膜電容器1的製造方法。以下，對具有由以組成式Aa Bb Oo Nn 表示的氮氧化物構成的主組成的介電質薄膜13中，A原子為Sr，且B原子為Ta的情況進行說明，但在使用其它種類的原子的情況下亦同。Method of Manufacturing Film Capacitor 1 Next, a method of manufacturing the film capacitor 1 will be described. Hereinafter, the case where the dielectric thin film 13 having the main composition composed of the nitrogen oxide represented by the composition formula A a B b O o N n is described as A atom being Sr and B atom being Ta, but The same is true when other types of atoms are used.

最終成為介電質薄膜13的薄膜的成膜方法沒有特別限制。例如，可以例示：真空蒸鍍法、濺射法、PLD法（脈衝雷射蒸鍍法）、MO-CVD（有機金屬化學氣相沉積法）、MOD（有機金屬分解法）、溶膠凝膠法、CSD（化學溶液堆積法）等。另外，有時在成膜時使用的原料中含有微少的雜質或副成分，但只要是不大幅損壞薄膜性能的程度的量，就沒有特別問題。另外，本實施方式的介電質薄膜13也可以在不大幅損壞性能的程度內含有微少的雜質或副成分。The method of forming the thin film that eventually becomes the dielectric thin film 13 is not particularly limited. For example, there can be exemplified: vacuum evaporation method, sputtering method, PLD method (pulse laser evaporation method), MO-CVD (organometallic chemical vapor deposition method), MOD (organometallic decomposition method), sol-gel method , CSD (Chemical Solution Stacking Method), etc. In addition, the raw materials used at the time of film formation may contain minute impurities or minor components, but there is no particular problem as long as the amount does not significantly impair the film performance. In addition, the dielectric thin film 13 of the present embodiment may contain a small amount of impurities or subsidiary components to the extent that the performance is not significantly impaired.

上述的成膜方法中，在藉由PLD法、濺射法及CSD法等的方法成膜時，最終得到的薄膜容易成為多晶膜。也能夠以CVD法合成，但由於成分元素數較多的關係，以PLD法或濺射法的組成控制性更高。在本實施方式中，說明利用PLD法的成膜方法。In the above-mentioned film forming method, when the film is formed by a method such as a PLD method, a sputtering method, a CSD method, or the like, the resulting thin film easily becomes a polycrystalline film. It can also be synthesized by the CVD method, but due to the large number of component elements, the composition controllability by the PLD method or the sputtering method is higher. In this embodiment, a film forming method using the PLD method will be described.

首先，作為基板11，準備Si單晶基板。接著，在Si單晶基板上，按照SiO2 、TiOx 、Pt的順序進行成膜，形成由Pt構成的下部電極12。形成下部電極12的方法沒有特別限制。例如，可以舉出濺射法或CVD法等。First, as the substrate 11, a Si single crystal substrate is prepared. Next, a film is formed on the Si single crystal substrate in the order of SiO 2 , TiO x , and Pt to form the lower electrode 12 made of Pt. The method of forming the lower electrode 12 is not particularly limited. For example, a sputtering method or a CVD method can be mentioned.

接著，在下部電極12上藉由PLD法將金屬氧化物薄膜成膜。為了使下部電極12的一部分露出，也可以使用金屬遮罩形成薄膜一部分未成膜的區域。Next, a metal oxide thin film is formed on the lower electrode 12 by the PLD method. In order to expose a part of the lower electrode 12, a metal mask may be used to form a region where a part of the thin film is not formed.

PLD法中，首先，將含有作為目標的介電質薄膜的構成元素的靶材設置於成膜室內。接著，向靶材的表面上照射脈衝雷射。藉由脈衝雷射較強的能量，使靶材的表面瞬間蒸發。然後，在以與靶材對向的方式配置的基板上沉積蒸發物，將金屬氧化物薄膜成膜。In the PLD method, first, a target material containing a constituent element of a target dielectric thin film is installed in a film forming chamber. Next, pulse laser is irradiated on the surface of the target. With the strong energy of the pulsed laser, the surface of the target material evaporates instantly. Then, an evaporant is deposited on the substrate arranged so as to face the target, and a metal oxide thin film is formed.

作為靶材，能夠使用例如具有組成式A2 B2 O7 的前驅物。此前驅物以被稱為鈣鈦礦板層之由鈣鈦礦單元和O過量層交替堆積而成的鈣鈦礦層狀化合物為佳。As the target material, for example, a precursor having a composition formula of A 2 B 2 O 7 can be used. Previously, the perovskite layered compound called perovskite plate layer consisting of perovskite units and O excess layers was alternately stacked.

靶材的種類沒有特別限制，也能夠使用將氮氧化物粉進行壓縮成型後的顆粒。但是，由於需要充分管理含有的N量，因此，使用A2 B2 O7 的顆粒時控制性良好。另外，靶材中各元素以平均地分佈為佳，但也可以在不影響得到的介電質薄膜的品質的範圍內分佈存在不均。此外，靶材未必需要為一個，也能夠準備多個含有介電質薄膜的構成元素的一部分的靶材並用於成膜。靶材的形狀也沒有限制，只要設為適於使用的成膜裝置的形狀即可。另外，藉由調整成膜條件（氧的氣壓、氮的氣壓、成膜室的大小及氣體導入管的位置等），能夠控制最終得到的介電質薄膜的a及b。例如，如果增大靶材的a/b，則能夠增大成膜後的膜中的a/b。The type of the target material is not particularly limited, and pellets obtained by compression molding of nitrogen oxide powder can also be used. However, since it is necessary to sufficiently manage the amount of N contained, the controllability is good when using A 2 B 2 O 7 particles. In addition, each element in the target is preferably distributed evenly, but there may be uneven distribution within a range that does not affect the quality of the obtained dielectric thin film. In addition, one target does not necessarily need to be one, and a plurality of targets containing a part of the constituent elements of the dielectric thin film can be prepared and used for film formation. The shape of the target material is also not limited, as long as it is a shape suitable for the film forming apparatus to be used. In addition, by adjusting the film forming conditions (pressure of oxygen, pressure of nitrogen, size of the film forming chamber, position of the gas introduction tube, etc.), a and b of the dielectric thin film finally obtained can be controlled. For example, if the a/b of the target is increased, the a/b in the film after film formation can be increased.

例如，在最終得到的介電質薄膜的組成為Sra Tab Oo Nn 的情況下，準備含有Sr2 Ta2 O7 的燒結體作為靶材。而且，藉由調整成膜條件（例如氧的氣壓、氮的氣壓、成膜室的大小及氣體導入管的位置等），能夠控制最終得到的介電質薄膜的a及b。For example, the dielectric composition film finally obtained is the case where Sr a Ta b O o N n, the sintered body is prepared which contains Sr 2 Ta 2 O 7 as a target. Furthermore, by adjusting the film-forming conditions (for example, the pressure of oxygen, the pressure of nitrogen, the size of the film-forming chamber, the position of the gas introduction tube, etc.), it is possible to control the a and b of the dielectric thin film finally obtained.

成膜條件也非常重要。原因是藉由脈衝雷射從靶材蒸發的金屬元素到達基板的成膜面，會受到構成成膜室中的環境的元素的影響的關係。從超高真空到大氣壓附近大範圍地設定環境壓力為PLD法的特徵，但真空度較高時容易得到結晶性高的膜，另一方面，氧等的環境壓力較高時容易得到氧等的缺陷較少的膜。在並用電漿的情況下，電漿決定能夠維持的壓力範圍寬度，因此，在此範圍內，只要鑒於結晶性及缺陷等決定適當的壓力即可。特別是在藉由PLD法成膜的情況下，總壓力以1×10-2 Pa以上為佳，以總壓力為2×10-2 Pa以上更佳。較佳的條件為真空度相對不高的條件。這是為了得到晶粒較小的膜而適當的條件，在此情況下，結晶性被評價為較低。此外，濺射法中，作為成膜室中的環境，併用氬為佳。成膜速率以30nm/min以下為佳，以10nm/min以下更佳。The film forming conditions are also very important. The reason is that the metal element evaporated from the target material by pulse laser reaches the film-forming surface of the substrate and is affected by the elements constituting the environment in the film-forming chamber. It is a characteristic of the PLD method to set the ambient pressure in a wide range from ultra-high vacuum to near atmospheric pressure, but it is easy to obtain a film with high crystallinity when the vacuum degree is high, and on the other hand, when the ambient pressure of oxygen and the like is high Membrane with fewer defects. When plasma is used in combination, the plasma determines the width of the pressure range that can be maintained. Therefore, within this range, it is sufficient to determine an appropriate pressure in consideration of crystallinity, defects, and the like. In particular, in the case of film formation by the PLD method, the total pressure is preferably 1×10 −2 Pa or more, and the total pressure is more preferably 2×10 −2 Pa or more. The preferred conditions are those where the vacuum is relatively low. This is an appropriate condition for obtaining a film with small crystal grains. In this case, the crystallinity is evaluated to be low. In addition, in the sputtering method, argon is preferably used as the environment in the film forming chamber. The film formation rate is preferably 30 nm/min or less, and more preferably 10 nm/min or less.

另外，在PLD法時，為了使成膜的金屬氧化物薄膜結晶化，在成膜時將基板11藉由紅外線雷射進行加熱為佳。成膜時的基板11的加熱溫度根據金屬氧化物薄膜及基板11的構成元素及組成等進行變化，但以550～850℃為佳，以600～800℃更佳。藉由將成膜時的基板的加熱溫度設為上述範圍，難以形成空隙，使介電特性提高。另外，藉由將基板11的溫度設為適當的溫度，金屬氮氧化物薄膜容易結晶化，並且能夠防止在冷卻時產生的裂紋的產生。In addition, in the PLD method, in order to crystallize the formed metal oxide thin film, it is preferable to heat the substrate 11 by infrared laser during the film formation. The heating temperature of the substrate 11 at the time of film formation varies depending on the metal oxide thin film, the constituent elements and composition of the substrate 11, and the like, but it is preferably 550 to 850°C, and more preferably 600 to 800°C. By setting the heating temperature of the substrate at the time of film formation to the above range, it is difficult to form voids and improve the dielectric characteristics. In addition, by setting the temperature of the substrate 11 to an appropriate temperature, the metal oxynitride thin film is easily crystallized, and the generation of cracks generated during cooling can be prevented.

在成膜中，藉由導入氮自由基進行氮化處理，能夠得到由鈣鈦礦型氮氧化物構成的介電質薄膜13。也可以在將金屬氧化物膜成膜後，導入氮自由基進行氮化處理，但在成膜中導入氮自由基時能夠進一步增加成膜後的薄膜中的氮量。In film formation, by introducing nitrogen radicals and performing nitridation treatment, a dielectric thin film 13 composed of perovskite-type nitrogen oxide can be obtained. After the metal oxide film is formed, nitrogen radicals may be introduced for nitriding treatment. However, when nitrogen radicals are introduced during film formation, the amount of nitrogen in the thin film after film formation can be further increased.

基板上的介電質薄膜13需要在成膜後進行高速熱退火處理（RTA）。為了使頻率特性更良好，需要將退火時的環境設為高於成膜環境的氧分壓及氮分壓。The dielectric thin film 13 on the substrate needs to be subjected to high-speed thermal annealing (RTA) after film formation. In order to improve the frequency characteristics, it is necessary to set the environment during annealing to be higher than the oxygen partial pressure and nitrogen partial pressure of the film formation environment.

最後，藉由在介電質薄膜13上形成上部電極14，能夠製造薄膜電容器1。此外，上部電極14的材質沒有特別限制，能夠使用Ag、Au、Cu等。另外，上部電極14的形成方法也沒有特別限制。例如，能夠藉由濺射法或蒸鍍形成。Finally, by forming the upper electrode 14 on the dielectric thin film 13, the thin film capacitor 1 can be manufactured. In addition, the material of the upper electrode 14 is not particularly limited, and Ag, Au, Cu, or the like can be used. In addition, the method of forming the upper electrode 14 is also not particularly limited. For example, it can be formed by sputtering or vapor deposition.

此外，也可以在介電質薄膜13與下部電極12之間、及介電質薄膜13與上部電極14之間具有中間層15。中間層15可以由絕緣材料構成，也可以由導電材料構成。作為絕緣材料，能夠使用含有鋁、矽、鍶及鉭中的至少一種的氧化物或氮化物等的化合物等。作為導電材料，能夠使用Cu、Al、Ni、Au及Ni-Cr等。作為中間層15的形成方法，能夠採用與上述的介電質薄膜13的形成方法、或下部電極12及上部電極14的形成方法同樣的方法。而且，中間層15可以作為絕緣層、應力緩衝層、或用於將電極面的凹凸平滑化的層等發揮作用。 中間層15可以處於介電質薄膜13與下部電極12之間、及介電質薄膜13與上部電極14之間兩者，也可以處於任一方。在中間層具有多個的情況下，各個中間層也可以具有不同的功能。 中間層15的厚度以介電質薄膜13的厚度的20%以下為佳，以10%以下更佳。In addition, an intermediate layer 15 may be provided between the dielectric thin film 13 and the lower electrode 12 and between the dielectric thin film 13 and the upper electrode 14. The intermediate layer 15 may be composed of an insulating material or a conductive material. As the insulating material, compounds containing oxides or nitrides of at least one of aluminum, silicon, strontium, and tantalum can be used. As the conductive material, Cu, Al, Ni, Au, Ni-Cr, and the like can be used. As a method for forming the intermediate layer 15, the same method as the method for forming the dielectric thin film 13 described above or the method for forming the lower electrode 12 and the upper electrode 14 can be used. Furthermore, the intermediate layer 15 may function as an insulating layer, a stress buffer layer, or a layer for smoothing irregularities on the electrode surface. The intermediate layer 15 may be located between the dielectric thin film 13 and the lower electrode 12 and between the dielectric thin film 13 and the upper electrode 14, or may be on either side. When there are a plurality of intermediate layers, each intermediate layer may have different functions. The thickness of the intermediate layer 15 is preferably 20% or less of the thickness of the dielectric thin film 13, and more preferably 10% or less.

本實施方式的介電質薄膜能夠用作例如能夠電壓同調的電容器、或如去耦薄膜電容器那樣的高密度電容器裝置的介電質層。The dielectric thin film of this embodiment can be used as a dielectric layer of a capacitor capable of voltage coherence, for example, or a high-density capacitor device such as a decoupling film capacitor.

本實施方式的電容元件為利用了本實施方式的介電質薄膜的優異的介電性的元件，包括電容器、熱敏電阻、濾波器、雙工器、諧振器、發射器、天線、壓電元件、電晶體、鐵電體記憶體等。本實施方式的介電質薄膜適用於特別是要求介電特性高的電容元件。The capacitive element of this embodiment is an element that uses the excellent dielectric properties of the dielectric thin film of this embodiment, and includes a capacitor, a thermistor, a filter, a duplexer, a resonator, a transmitter, an antenna, a piezoelectric Components, transistors, ferroelectric memory, etc. The dielectric thin film of this embodiment is particularly suitable for a capacitor element that requires high dielectric characteristics.

作為本實施方式的電容元件，作為例如電容器的製造方法，可以舉出在基板上形成具有適當的電極的高同調裝置結構的方法。作為該高同調裝置結構，沒有特別限定，例如也可以使用與SAW(Surface Acoustic Wave)雙工器、利用RF-MEMS(radio frequency microelectromechanical system)的開關、壓電驅動型的MEMS氣隙可變電抗器、固定（低同調性）高密度薄膜電容器、TFBAR(Thin Film Bulk Acoustic Resonator)電路、電阻器、電感器、以氧化物為基體的TFT(Thin Film Transistor)及感測器等其它薄膜裝置集成化後的裝置結構。As the capacitive element of the present embodiment, for example, as a method of manufacturing a capacitor, a method of forming a high coherence device structure having appropriate electrodes on a substrate can be mentioned. The structure of the highly coherent device is not particularly limited, and for example, a SAW (Surface Acoustic Wave) duplexer, a switch using RF-MEMS (radio frequency microelectromechanical system), or a piezoelectric drive type MEMS air gap variable power can also be used Reactors, fixed (low coherence) high-density film capacitors, TFBAR (Thin Film Bulk Acoustic Resonator) circuits, resistors, inductors, oxide-based TFT (Thin Film Transistor) and sensors and other thin film devices Integrated device structure.

以上，說明瞭本發明的實施方式，但本發明不被限定於這樣的實施方式，當然可以在不脫離本發明的要點的範圍內以各種不同的方式進行實施。 實施例The embodiments of the present invention have been described above, but the present invention is not limited to such embodiments, and can of course be implemented in various different ways without departing from the gist of the present invention. Examples

以下，基於更詳細的實施例來說明本發明，但本發明不限定於這些實施例。Hereinafter, the present invention will be described based on more detailed examples, but the present invention is not limited to these examples.

實施例1 首先，作為用作成膜用靶材的Sr2 Ta2 O7 燒結體的原料，準備SrCO3 粉末及Ta2 O5 粉末。以Sr/Ta的莫爾比成為1的方式稱量SrCO3 粉末及Ta2 O5 粉末。Example 1 First, as a raw material of a Sr 2 Ta 2 O 7 sintered body used as a target for film formation, SrCO 3 powder and Ta 2 O 5 powder were prepared. The SrCO 3 powder and Ta 2 O 5 powder were weighed so that the Sr/Ta molar ratio became 1.

接著，對於SrCO3 粉末及Ta2 O5 粉末，利用使用了乙醇溶劑的濕式球磨機混合16小時，得到混合漿料。Next, the SrCO 3 powder and Ta 2 O 5 powder were mixed for 16 hours using a wet ball mill using an ethanol solvent to obtain a mixed slurry.

接著，將上述混合漿料利用恆溫乾燥機以80℃乾燥12小時，得到混合物。Next, the above mixed slurry was dried at 80° C. for 12 hours using a constant temperature dryer to obtain a mixture.

接著，將上述混合物在乳缽中輕微粉碎，並放入陶瓷制的坩堝中。然後，使用電爐在大氣環境中以1000℃進行2小時熱處理，得到預燒物。Next, the above mixture was slightly crushed in a mortar and placed in a ceramic crucible. Then, an electric furnace was used to perform heat treatment at 1000°C for 2 hours in an atmospheric environment to obtain a pre-fired product.

接著，對於上述預燒物，再次利用使用了乙醇溶劑的濕式球磨機混合16小時，得到預燒後漿料。Next, the calcined product was mixed again with a wet ball mill using an ethanol solvent for 16 hours to obtain a calcined slurry.

將得到的預燒後漿料利用恆溫乾燥機以80℃乾燥12小時，得到預燒後混合物。The obtained calcined slurry was dried at 80° C. for 12 hours using a constant temperature dryer to obtain a calcined mixture.

對於上述預燒後混合物，添加作為黏合劑的聚乙烯醇溶液，並進行混合，得到造粒物。聚乙烯醇溶液的添加量相對於粉碎物100重量%設為0.6重量%。To the above-mentioned pre-calcined mixture, a polyvinyl alcohol solution as a binder is added and mixed to obtain a granulated material. The addition amount of the polyvinyl alcohol solution was set to 0.6% by weight based on 100% by weight of the pulverized product.

將上述造粒物成型為直徑約23mm、高度約9mm的圓柱形狀，得到成型物。成型方法設為CIP成型。The granulated material was molded into a cylindrical shape with a diameter of about 23 mm and a height of about 9 mm to obtain a molded product. The molding method is CIP molding.

對於上述成型物，使用電爐在大氣環境中，以1400℃燒成2小時，得到燒結物。進一步，將上述燒結物的上表面及下表面進行鏡面研磨，得到高度5mm的成膜靶材。此外，確認了得到的成膜靶材的相對密度為96～98%。The above molded product was fired at 1400°C for 2 hours in an atmospheric environment using an electric furnace to obtain a sintered product. Furthermore, the upper surface and the lower surface of the sintered product were mirror-polished to obtain a film-forming target with a height of 5 mm. In addition, it was confirmed that the relative density of the obtained film-forming target material was 96 to 98%.

將如上所述得到的成膜用靶材設置於成膜裝置中，以與成膜用靶材對向的方式設置Si基板。作為此Si基板，使用了在表面具有作為下部電極的Pt膜的基板。The target for film formation obtained as described above was set in a film forming apparatus, and a Si substrate was provided so as to face the target for film forming. As this Si substrate, a substrate having a Pt film as a lower electrode on the surface is used.

實施例1中，藉由PLD法以厚度成為1000nm的方式成膜。此時，向成膜室導入氮自由基，形成介電質氧化膜。成膜時的環境的氮分壓設為1×10-3 Pa。成膜溫度設為700℃。成膜後，停止氮自由基的導入，同時導入氮及氧，以700℃進行30分鐘退火。然後，冷卻至200℃，將環境設為真空，得到介電質薄膜樣品。對於得到的介電質薄膜樣品，如下進行評價。In Example 1, a film was formed with a thickness of 1000 nm by the PLD method. At this time, nitrogen radicals are introduced into the film forming chamber to form a dielectric oxide film. The nitrogen partial pressure in the environment during film formation was set to 1×10 -3 Pa. The film formation temperature was set to 700°C. After the film formation, the introduction of nitrogen radicals was stopped, nitrogen and oxygen were simultaneously introduced, and annealing was performed at 700°C for 30 minutes. Then, it cooled to 200 degreeC, the environment was set to vacuum, and the dielectric thin film sample was obtained. The obtained dielectric thin film samples were evaluated as follows.

多晶膜及其取向性的評價 對於得到的樣品，進行XRD測定，根據其XRD圖案確認是否為向特定的面取向的取向膜和是否具有多晶性。在具有多晶性，且不是相對於特定的面取向的取向膜的情況下，評價為“良”，在不具有多晶性的情況及為取向膜的情況下，評價為“不良”。另外，使用ULVAC-PHI, Inc.製造的PHI Quantera IITM並藉由光電子分光分析，對得到的薄膜樣品所包含的氮氧化物的組成定量。一邊進行Ar蝕刻，一邊對薄膜的深度方向的組成定量。Evaluation of Polycrystalline Film and Orientation The obtained sample was subjected to XRD measurement, and based on its XRD pattern, it was confirmed whether it was an oriented film oriented to a specific plane and whether it had polymorphism. When it is polycrystalline and is not oriented to a specific plane, it is evaluated as "good", and when it is not polycrystalline and when it is an oriented film, it is evaluated as "poor". In addition, using PHI Quantera IITM manufactured by ULVAC-PHI, Inc. and photoelectron spectroscopic analysis, the composition of the nitrogen oxide contained in the obtained thin film sample was quantified. While performing Ar etching, the composition in the depth direction of the film was quantified.

利用TEM的晶粒的尺寸測定 對於得到的樣品，使用透射電子顯微鏡（TEM）得到TEM圖像。將得到的TEM圖像在圖4中表示。基於圖4所示的TEM圖像，測定晶粒的尺寸。另外，使用TEM確認柱狀的顆粒的有無。將結果在表1中表示。Measurement of the size of crystal grains by TEM For the obtained sample, a TEM image was obtained using a transmission electron microscope (TEM). The obtained TEM image is shown in FIG. 4. Based on the TEM image shown in FIG. 4, the size of crystal grains was measured. In addition, the presence or absence of columnar particles was confirmed using TEM. Table 1 shows the results.

利用XRD的晶粒的尺寸測定 對於得到的樣品，藉由面外法及面內法進行X射線繞射測定，測定晶粒的尺寸。Measurement of crystal grain size by XRD For the obtained sample, X-ray diffraction measurement was performed by an out-of-plane method and an in-plane method to measure the size of the crystal grain.

相對介電常數ε的測定 相對介電常數（ε）在電壓1Vrms/μm、頻率20Hz～10kHz下進行評價，算出其變化率。用於評價相對介電常數的上部電極，是藉由以直徑100μm的尺寸蒸鍍Ag而形成。將結果在表1中表示。Measurement of relative dielectric constant ε The relative dielectric constant (ε) was evaluated at a voltage of 1 Vrms/μm and a frequency of 20 Hz to 10 kHz, and the rate of change was calculated. The upper electrode for evaluating the relative dielectric constant is formed by vapor-depositing Ag with a diameter of 100 μm. Table 1 shows the results.

相對介電常數變化率Δε的測定 對於形成有上述Ag電極的樣品，測定相對介電常數變化率Δε。相對介電常數變化率Δε藉由以頻率20Hz及10kHz測得的相對介電常數的差，除以以頻率20Hz測得的相對介電常數而算出。Measurement of Relative Permittivity Change Rate Δε For the sample formed with the Ag electrode, the relative permittivity change rate Δε was measured. The relative permittivity change rate Δε is calculated by dividing the difference in relative permittivity measured at frequencies 20 Hz and 10 kHz by the relative permittivity measured at frequency 20 Hz.

實施例2～4 除了控制成膜時的環境，將利用XRD得到的晶粒的尺寸調整成表1所示以外，與實施例1同樣地進行，得到介電質薄膜樣品。與實施例1同樣地評價。Examples 2 to 4 The dielectric thin film samples were obtained in the same manner as in Example 1 except that the environment during film formation was controlled and the size of crystal grains obtained by XRD was adjusted as shown in Table 1. Evaluation was performed in the same manner as in Example 1.

實施例5 除了以下所示以外，與實施例3同樣地進行，得到介電質薄膜樣品。即，實施例5中，作為用於成膜用靶材的(La0.1 Sr0.9 )2 (Ta0.9 Ti0.1 )2 O7 燒結體的原料，準備La2 O3 粉末、SrCO3 粉末、Ta2 O5 粉末及TiO2 粉末。以(La0.1 Sr0.9 )/(Ta0.9 Ti0.1 )的莫爾比成為1的方式稱量La2 O3 粉末、SrCO3 粉末、Ta2 O5 粉末及TiO2 粉末。Example 5 A dielectric thin film sample was obtained in the same manner as in Example 3 except for the following. That is, in Example 5, as the raw material of the (La 0.1 Sr 0.9 ) 2 (Ta 0.9 Ti 0.1 ) 2 O 7 sintered body for the film-forming target, La 2 O 3 powder, SrCO 3 powder, Ta 2 were prepared O 5 powder and TiO 2 powder. The La 2 O 3 powder, SrCO 3 powder, Ta 2 O 5 powder, and TiO 2 powder were weighed so that the molar ratio of (La 0.1 Sr 0.9 )/(Ta 0.9 Ti 0.1 ) became 1.

實施例6 除了以下所示以外，與實施例3同樣地進行，得到介電質薄膜樣品。即，實施例6中，作為用於成膜用靶材的(Ba0.2 Sr0.8 )2 Ta2 O7 燒結體的原料，準備BaCO3 粉末、SrCO3 粉末及Ta2 O5 粉末。以(Ba0.2 Sr0.8 )/(Ta)的莫爾比成為1的方式稱量BaCO3 粉末、SrCO3 粉末及Ta2 O5 粉末。已知Sr2 Ta2 O7 的組合物作為具有鈣鈦礦板層結構的燒結體存在，與之相對，不存在Ba2 Ta2 O7 。但是，藉由以(Ba0.2 Sr0.8 )/(Ta)的莫爾比成為1的方式稱取及配合BaCO3 粉末、SrCO3 粉末及Ta2 O5 粉末，能夠得到(Ba0.2 Sr0.8 )2 Ta2 O7 組成的燒結體。得到的燒結體與Sr2 Ta2 O7 相同，具有X射線繞射圖案，其波峰位置偏移向低角度側。Example 6 A dielectric thin film sample was obtained in the same manner as in Example 3 except for the following. That is, in Example 6, as the raw material of the (Ba 0.2 Sr 0.8 ) 2 Ta 2 O 7 sintered body for the film-forming target, BaCO 3 powder, SrCO 3 powder, and Ta 2 O 5 powder were prepared. The BaCO 3 powder, SrCO 3 powder, and Ta 2 O 5 powder were weighed so that the molar ratio of (Ba 0.2 Sr 0.8 )/(Ta) became 1. It is known that the composition of Sr 2 Ta 2 O 7 exists as a sintered body having a perovskite lamellar structure, whereas Ba 2 Ta 2 O 7 does not exist. However, by weighing and mixing BaCO 3 powder, SrCO 3 powder and Ta 2 O 5 powder so that the molar ratio of (Ba 0.2 Sr 0.8 )/(Ta) becomes 1, it is possible to obtain (Ba 0.2 Sr 0.8 ) 2 A sintered body composed of Ta 2 O 7 . The obtained sintered body has the same Xr-ray diffraction pattern as Sr 2 Ta 2 O 7 and its peak position is shifted to the low angle side.

比較例1 比較例1根據非專利文獻1進行算出。非專利文獻1中，藉由使用了氮電漿輔助脈衝雷射沉積法的磊晶成長，形成SrTaO2 N的薄膜結晶樣品。具體而言，作為結晶成長用的基板，使用晶格常數比SrTaO2 N小的鈮添加鈦酸鍶（Nb：SrTiO3 ）單晶，使照射紫外雷射而氣化的鉭酸鍶（Sr2 Ta2 O7 ）和由電漿活化的氮在基板上進行反應。與實施例1同樣地評價。將結果在表1中表示。Comparative Example 1 Comparative Example 1 was calculated based on Non-Patent Document 1. In Non-Patent Document 1, a thin film crystal sample of SrTaO 2 N is formed by epitaxial growth using a nitrogen plasma assisted pulsed laser deposition method. Specifically, as a substrate for crystal growth, niobium with a lattice constant smaller than SrTaO 2 N is added, and strontium titanate (Nb: SrTiO 3 ) single crystal is added, and strontium tantalate (Sr 2 Ta 2 O 7 ) and plasma-activated nitrogen react on the substrate. Evaluation was performed in the same manner as in Example 1. Table 1 shows the results.

實施例7～12 實施例7～12中，除了改變成膜時的環境的氮分壓進行成膜以外，與實施例1同樣地進行，得到介電質薄膜樣品。與實施例1同樣地評價。將結果在表1中表示。Examples 7-12 In Examples 7-12, except having changed the nitrogen partial pressure of the environment at the time of film formation and performing film formation, it carried out similarly to Example 1, and obtained the dielectric thin film sample. Evaluation was performed in the same manner as in Example 1. Table 1 shows the results.

表1

Figure 107111242-A0304-0001
Table 1
Figure 107111242-A0304-0001

根據表1，實施例1～12中，得到由作為未向特定的晶面方向取向的多晶的結晶粒子構成的介電質薄膜樣品，並且具有優異的介電特性。另一方面，在比較例1的介電質薄膜樣品中，確認了結晶粒子所包含的晶粒的尺寸超過100nm，相對介電常數相對於頻率的變化率較差。According to Table 1, in Examples 1 to 12, dielectric thin film samples composed of polycrystalline crystal particles that were not oriented in a specific crystal plane direction were obtained, and they had excellent dielectric properties. On the other hand, in the dielectric thin film sample of Comparative Example 1, it was confirmed that the size of crystal grains included in the crystal particles exceeds 100 nm, and the rate of change of the relative dielectric constant with frequency is poor.

1‧‧‧薄膜電容器11‧‧‧基板12‧‧‧下部電極13‧‧‧介電質薄膜14‧‧‧上部電極15‧‧‧中間層X‧‧‧結晶粒子Y‧‧‧晶粒R‧‧‧入射X射線R’‧‧‧繞射X射線1‧‧‧film capacitor 11‧‧‧substrate 12‧‧‧lower electrode 13‧‧‧dielectric thin film 14‧‧‧upper electrode 15‧‧‧interlayer X‧‧‧crystal particles Y‧‧‧grain R ‧‧‧Incident X-ray R'‧‧‧diffracted X-ray

11

圖1是本發明的一個實施方式的薄膜電容器的概略圖。 圖2是表示本發明的一個實施方式的介電質薄膜的結晶粒子所包含的晶粒的形狀的示意圖。 圖3（a）是表示利用面外法的X射線繞射測定的示意圖。 圖3（b）是表示利用面內法的X射線繞射測定的示意圖。 圖4是實施例1的介電質薄膜樣品的TEM圖像，虛線表示晶粒的形狀。FIG. 1 is a schematic diagram of a film capacitor according to an embodiment of the present invention. 2 is a schematic diagram showing the shape of crystal grains included in crystal particles of a dielectric thin film according to an embodiment of the present invention. FIG. 3( a) is a schematic diagram showing X-ray diffraction measurement by the out-of-plane method. FIG. 3( b) is a schematic diagram showing X-ray diffraction measurement by the in-plane method. 4 is a TEM image of the dielectric thin film sample of Example 1, and the broken line indicates the shape of the crystal grain.

1‧‧‧薄膜電容器 1‧‧‧ film capacitor

11‧‧‧基板 11‧‧‧ substrate

12‧‧‧下部電極 12‧‧‧Lower electrode

13‧‧‧介電質薄膜 13‧‧‧Dielectric film

14‧‧‧上部電極 14‧‧‧Upper electrode

15‧‧‧中間層 15‧‧‧ middle layer

Claims (4)

一種介電質薄膜，係具有由組成式AaBbOoNn表示的氮氧化物構成的主組成，其中，a+b+o+n=5，a<1，a/b>1或a/b≧1.05，1>n>0或1>n≧0.3或1>n≧0.5的介電質薄膜，其特徵在於，上述A為Sr、Ba、Ca、La、Ce、Pr、Nd、Na的任意一種以上，上述B為Ta、Nb、Ti、W的任意一種以上，構成上述介電質薄膜的結晶粒子為未向某特定的晶面方向取向的多晶，上述介電質薄膜所包含的結晶粒子的晶粒的尺寸為100nm以下。 A dielectric thin film having a main composition composed of nitrogen oxides represented by the composition formula A a B b O o N n , where a+b+o+n=5, a<1, a/b>1 Or a/b≧1.05, 1>n>0 or 1>n≧0.3 or 1>n≧0.5 dielectric thin film, characterized in that the above A is Sr, Ba, Ca, La, Ce, Pr, Nd , Any one or more of Na, and the above B is any one or more of Ta, Nb, Ti, and W, the crystal particles constituting the dielectric thin film are polycrystals that are not oriented in a certain crystal plane direction, and the dielectric thin film The crystal grain size of the included crystal particles is 100 nm or less. 如申請專利範圍第1項所述的介電質薄膜，對於上述介電質薄膜，基於藉由面外法進行X射線繞射測定得到的結果算出的晶粒的尺寸為基於藉由面內法進行X射線繞射測定得到的結果算出的晶粒的尺寸的1.5倍以上。 The dielectric thin film as described in item 1 of the patent application scope, for the dielectric thin film, the size of the crystal grain calculated based on the result of X-ray diffraction measurement by the out-of-plane method is based on the in-plane method The size of the crystal grain calculated based on the results of X-ray diffraction measurement is 1.5 times or more. 如申請專利範圍第1或2項所述的介電質薄膜，上述A為Sr，上述B為Ta及/或Nb，上述n大於0且小於1。 According to the dielectric thin film described in item 1 or 2 of the patent application, the A is Sr, the B is Ta and/or Nb, and the n is greater than 0 and less than 1. 一種電容元件，具有如申請專利範圍第1~3項中任一項所述的介電質薄膜。A capacitive element having the dielectric thin film as described in any of items 1 to 3 of the patent application.
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１、I. Marozau et al., 2011. Pulsed laser deposition and characterization of perovskite-type LaTiO3-xNx thin films, Acta Materialia, Vol. 59, page: 7145-7154. Daichi Oka et al., 2014. Possible ferroelectricity in perovskite oxynitride SrTaO2N epitaxial thin films, Scientific Reports, Vol. 4, page: 1-6. *
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