JP3819003B2 - Capacitor element and manufacturing method thereof - Google Patents

Description

  The present invention relates to a capacitive element using a ferroelectric film having a bismuth layer structure and a method for manufacturing the same.

  In recent years, along with the advancement of digital technology, electronic devices have become more sophisticated while the tendency to process and store large amounts of data has been promoted, and semiconductor devices used in electronic devices have also become finer. Is progressing rapidly.

  Along with miniaturization of semiconductor elements, in order to realize higher integration of DRAM (Dynamic Random Access Memory), a dielectric having a high dielectric constant (hereinafter referred to as “high dielectric”) is used instead of conventional silicon oxide or silicon nitride. The technology that uses the body as a capacitor film of a storage capacitor has been widely researched and developed.

  Furthermore, research on FeRAM (Ferroelectric Random Access Memory) using a ferroelectric material with spontaneous polarization characteristics, aiming at the practical application of non-volatile memory that operates at a low voltage and that can be written and read at high speed. Development is actively underway.

  At present, FeRAM has a small capacity memory in practical use, but in order to realize a further increase in capacity, a structure in which a capacitive element is formed on the contact plug formed in the source region or drain region of the access transistor. A stack type memory cell having the above has been developed.

  In a stack type memory cell, a capacitive element is formed on a plug made of polysilicon or tungsten, but an oxygen barrier film is used for the purpose of preventing oxidation of the plug. For the oxygen barrier film, a conductive oxide of a platinum group metal such as iridium oxide is usually used as a material. However, since these materials generally have high generation energy, oxygen is easily released during high-temperature heat treatment or easily reacts with other elements. Therefore, an oxygen barrier film made of these materials. Has the problem of having an unstable state.

  Conventionally, a method for stabilizing the oxygen barrier film by adding a small amount of a metal oxide having a strong bond with oxygen to the oxygen barrier film has been proposed (for example, Patent Document 1). And 2).

  Patent Document 1 discloses a diffusion prevention layer in which a small amount of rare earth elements such as Y, Ce, Dy, and Gd and oxygen are added to platinum group metals such as Pt, Ir, Ru, Rh, and Pd.

  In Patent Document 2, there is a diffusion prevention layer formed by adding a small amount of transition metal such as Ta, Zr, Nb, V, Mo, W and oxygen to platinum group metals of Pt, Ir, Ru, Rh, and Pd. It is disclosed. Since rare earth elements and transition metals have strong bonds with oxygen, stable compounds are formed.

On the other hand, as the capacity film of FeRAM, SrBi ₂ Ta ₂ O ₉ (commonly known as SBT), SrBi ₂ Nb ₂ O ₉ (commonly known as SBN), SrBi ₂ (Ta _1−x Nb _x ) ₂ O ₉ (however, 0 <x < 1, commonly known as SBTN), Bi _3.25 La _0.75 Ti ₃ O ₁₂ (commonly known as BLT), etc. are often used. These materials are collectively referred to as a ferroelectric having a bismuth layer structure (hereinafter referred to as a bismuth layer structure ferroelectric) and represented by the following chemical formula (1).

(Bi ₂ O ₂ ) ²⁺ (A _m-1 B _m O _{3m + 1} ) ²⁻ (m = 1, 2, 3...) (1)
However, A is a 1, 2, or 3 valent metal, B is a 4, 5 or 6 valent metal.

The crystal structure of the bismuth layered structure ferroelectric is a layered structure in which bismuth oxide layers (Bi ₂ O ₂ ) and pseudo-perovskite layers (A _m-1 B _m O _{3m + 1} ) are alternately stacked. A major feature obtained by these structures is a phenomenon called film fatigue in which the polarization amount decreases when a large number of polarization inversions are repeated, or a phenomenon called imprint in which the polarization amount in the reverse direction decreases when the polarization state on one side is maintained. This is unlikely to occur as compared with a normal perovskite structure. This is because (a) the distortion of the crystal lattice accompanying the polarization inversion of the pseudo-perovskite layer is absorbed by the bismuth oxide layer, and (b) the generation of oxygen vacancies in the pseudo-perovskite layer is compensated by oxygen in the bismuth oxide layer. It is thought to be from. Thus, by using a bismuth layered structure ferroelectric having excellent properties for the capacitor film, an FeRAM having excellent reliability can be realized.
Japanese Patent Laid-Open No. 10-242408 JP-A-10-242409

  However, since the bismuth layer structure ferroelectric has unstable bismuth as a constituent element, the composition shift of the bismuth layer structure ferroelectric is caused by bismuth being released from the bismuth layer structure ferroelectric during film formation. There is a problem that occurs.

  The reason why the bismuth contained in the bismuth layer structure ferroelectric is unstable is that (a) bismuth is easily melted because of its low melting point, and (b) bismuth oxide is easily generated because of its high generation energy. It is because it reduces. For example, when a bismuth layer-structured ferroelectric film is formed using metalorganic chemical vapor deposition, a part of bismuth is melted during deposition and during heat treatment for crystallization after deposition. And reduce and diffuse to the electrode. As a result, the lack of bismuth in the bismuth layered structure ferroelectric causes precipitation of the pyrochlore phase, crystal defects, or vacancies. When a capacitor element having a bismuth layered structure ferroelectric film in which a pyrochlore phase or the like is deposited, crystal defects or vacancies is formed, an increase in leakage current, deterioration in breakdown voltage, deterioration in film fatigue characteristics, and imprint characteristics Deterioration occurs.

  Here, the reason why the pyrochlore phase precipitates when bismuth is insufficient in the bismuth layer structure ferroelectric will be briefly described.

  Since the bismuth layer structure is represented by the chemical formula (1) as described above, the composition ratio of Bi and A site metal to the B site metal is larger than 1 as shown in the following general formula (2). Have

(Bi + A) / B = (m + 1) / m> 1 (2)
On the other hand, the structure of the pyrochlore phase has the following chemical formula (3)
(Bi, A) ₂ B ₂ O ₇ (3)
Therefore, the composition ratio of Bi and A site metal to B site metal is 1 as shown in the following general formula (4).

(Bi + A) / B = 1 (4)
Therefore, when bismuth is insufficient, the value of (Bi + A) / B decreases and approaches 1 so that a part of the crystal phase of the film becomes a pyrochlore phase.

  When a bismuth layered structure ferroelectric film is used for a stack type memory cell, a platinum group metal conductive oxide film having a function as an oxygen barrier is usually used for a capacitor lower electrode. However, even in this case, it is not easy to stop the diffusion of bismuth from the bismuth layered structure ferroelectric film. This is because the conductive oxide film of a platinum group metal is a polycrystalline film and has many grain boundaries, and bismuth easily diffuses through the grain boundaries.

  Moreover, even when a method of adding a small amount of rare earth element or transition metal oxide to the platinum group metal oxide film as in the above-described conventional example, the rare earth element or transition metal precipitated at the grain boundary is used. It is difficult to stop diffusion due to the easy reaction between bismuth and bismuth.

  In view of the above, an object of the present invention is to provide a capacitive element that prevents bismuth from escaping from a capacitive film made of a bismuth layer-structured ferroelectric film and does not cause a composition shift of the bismuth layer-structured ferroelectric, and a method for manufacturing the same It is to be. Thus, a capacitive element that can suppress deterioration of characteristics of the capacitive element such as an increase in leakage current, deterioration of breakdown voltage, deterioration of film fatigue characteristics and imprint characteristics, and a method for manufacturing the same are provided.

  In order to solve the above-described problems, a first capacitor element according to the present invention includes a diffusion prevention layer, a capacitor lower electrode formed on the diffusion prevention layer, and a bismuth layer formed on the capacitor lower electrode. A capacitor film made of a ferroelectric material having a structure and a capacitor upper electrode formed on the capacitor film, and the diffusion prevention layer is made of a material in which bismuth oxide is added to a conductive metal oxide. And

  According to the first capacitive element, a diffusion prevention layer made of a material in which bismuth oxide is added to a conductive metal oxide is formed under the capacitance lower electrode, and bismuth is present in the diffusion prevention layer in advance. Therefore, diffusion of bismuth from the capacitive film that occurs when the capacitive film is formed can be prevented by the diffusion preventing layer. As a result, it is possible to prevent the compositional deviation of the capacitor film caused by the bismuth from escaping from the capacitor film made of a ferroelectric material having a bismuth layered structure, thereby increasing the leakage current, deterioration of the breakdown voltage, film fatigue characteristics and imprint characteristics. It is possible to suppress deterioration of the characteristics of the capacitive element such as deterioration of the capacitor.

  In the first capacitor element, the molar fraction of bismuth with respect to all metals contained in the diffusion preventing layer is preferably larger than the molar fraction of bismuth with respect to all metals contained in the capacitor lower electrode.

  In this case, a gradient is generated in the molar fraction of bismuth between the diffusion preventing layer and the capacitor lower electrode. In general, since diffusion from a low mole fraction side to a high side is suppressed, diffusion of bismuth from the capacitor film that occurs when the capacitor film is formed can be more reliably prevented by the diffusion preventing layer. Thereby, it is possible to more reliably prevent the compositional deviation of the capacitive film caused by the bismuth being released from the capacitive film made of a ferroelectric having a bismuth layer structure.

  A second capacitive element according to the present invention is formed on a capacitive lower electrode made of a diffusion preventing layer, a capacitive film made of a ferroelectric having a bismuth layer structure formed on the capacitive lower electrode, and on the capacitive film. The diffusion prevention layer is preferably made of a material obtained by adding bismuth oxide to a conductive metal oxide.

  According to the second capacitor element, a capacitor lower electrode composed of a diffusion prevention layer made of a material in which bismuth oxide is added to a conductive metal oxide is formed under the capacitance film. Since bismuth is present in advance, diffusion of bismuth from the capacitor film that occurs when the capacitor film is formed can be prevented by the diffusion preventing layer. As a result, it is possible to prevent the compositional deviation of the capacitor film caused by the bismuth from escaping from the capacitor film made of a ferroelectric material having a bismuth layered structure, thereby increasing the leakage current, deterioration of the breakdown voltage, film fatigue characteristics and imprint characteristics. It is possible to suppress deterioration of the characteristics of the capacitive element such as deterioration of the capacitor. Furthermore, since the diffusion preventing layer prevents bismuth from escaping from the capacitor film and also serves as a capacitor lower electrode, the structure of the capacitor element is simplified and the capacitor element can be easily formed. .

  In the second capacitive element, it is preferable that the molar fraction of bismuth with respect to all metals contained in the diffusion preventing layer is larger than the molar fraction of bismuth with respect to all metals contained in the capacitive film.

  In this way, a gradient occurs in the molar fraction of bismuth between the diffusion preventing layer and the capacitive film. In general, since diffusion from a low mole fraction side to a high side is suppressed, diffusion of bismuth from the capacitor film that occurs when the capacitor film is formed can be more reliably prevented by the diffusion preventing layer. Thereby, it is possible to more reliably prevent the compositional deviation of the capacitive film caused by the bismuth being released from the capacitive film made of a ferroelectric having a bismuth layer structure.

  In the first or second capacitor element, it is preferable that the diffusion prevention layer has a polycrystalline structure of a conductive metal oxide, and bismuth oxide is precipitated at grain boundaries of the polycrystalline structure.

  In this case, since bismuth oxide is precipitated at the grain boundaries of the polycrystalline structure, bismuth from the capacitive film can be prevented from diffusing at high speed through the grain boundaries of the polycrystalline structure. Diffusion can be more reliably prevented by the diffusion preventing layer. Thereby, it is possible to more reliably prevent the compositional deviation of the capacitive film caused by the bismuth being released from the capacitive film made of a ferroelectric having a bismuth layer structure.

In the first or second capacitor element, the conductive metal oxide is preferably an oxide of a platinum group metal, and the diffusion prevention layer has the following composition formula: MptO ₂ + x · BiO _2/3
(However, Mpt is a platinum group metal and x satisfies the relational expression 0.05 <x <0.5).

  In this way, it is possible to prevent a displacement in the composition of the capacitive film caused by the bismuth being released from the capacitive film made of a ferroelectric having a bismuth layer structure.

In the first or second capacitor element, the conductive metal oxide is preferably a conductive perovskite oxide, and the diffusion prevention layer has the following composition formula: MaMbO ₃ + 2 · x · BiO _{2 / Three}
(However, Ma is one or more metals selected from monovalent, divalent or trivalent metals, Mb is a metal capable of 6 coordination, and x is 0.05 <x <0.5. It is more preferable that the relational expression is satisfied.

  In this way, not only can bismuth from the capacitive film diffuse at high speed through the grain boundaries of the polycrystalline structure, but also bismuth can be prevented from being absorbed by the conductive metal oxide. The diffusion preventing layer can more reliably prevent bismuth from being diffused. Thereby, it is possible to more reliably prevent the compositional deviation of the capacitive film caused by the bismuth being released from the capacitive film made of a ferroelectric having a bismuth layer structure.

In the first or second capacitor element, the conductive metal oxide is preferably a conductive pyrochlore oxide, and the diffusion prevention layer has the following composition formula: Ma ₂ Mb ₂ O ₇ + 4 · x・ BiO _2/3
(However, Ma is one or more metals selected from monovalent, divalent or trivalent metals, Mb is a metal capable of 6 coordination, and x is 0.05 <x <0.5. It is preferable that the relational expression is satisfied.

  In this way, not only can bismuth from the capacitive film diffuse at high speed through the grain boundaries of the polycrystalline structure, but also bismuth can be prevented from being absorbed by the conductive metal oxide. The diffusion preventing layer can more reliably prevent bismuth from being diffused. Thereby, it is possible to more reliably prevent the compositional deviation of the capacitive film caused by the bismuth being released from the capacitive film made of a ferroelectric having a bismuth layer structure.

  The first method for manufacturing a capacitive element according to the present invention includes a step of forming a diffusion prevention layer made of a material in which bismuth oxide is added to a conductive metal oxide on a substrate; Forming a capacitor lower electrode; forming a capacitor film made of a ferroelectric material having a bismuth layer structure on the capacitor lower electrode; and forming a capacitor upper electrode on the capacitor film. It is characterized by.

  According to the first method of manufacturing a capacitor element, a diffusion prevention layer made of a material in which bismuth oxide is added to a conductive metal oxide is formed under the capacitor lower electrode, and bismuth exists in advance in the diffusion prevention layer. Therefore, diffusion of bismuth from the capacitor film that occurs when the capacitor film is formed can be prevented by the diffusion preventing layer. As a result, it is possible to prevent the compositional deviation of the capacitor film caused by the bismuth from escaping from the capacitor film made of a ferroelectric material having a bismuth layered structure, thereby increasing the leakage current, deterioration of the breakdown voltage, film fatigue characteristics and imprint characteristics. It is possible to suppress deterioration of the characteristics of the capacitive element such as deterioration of the capacitor.

  The second method for manufacturing a capacitive element according to the present invention includes a step of forming, on a substrate, a capacitive lower electrode composed of a diffusion prevention layer made of a material in which bismuth oxide is added to a conductive metal oxide, The method includes a step of forming a capacitor film made of a ferroelectric material having a bismuth layer structure on the lower electrode, and a step of forming a capacitor upper electrode on the capacitor film.

  According to the second method of manufacturing a capacitor element, a capacitor lower electrode composed of a diffusion prevention layer made of a material obtained by adding bismuth oxide to a conductive metal oxide is formed under the capacitance film, thereby preventing diffusion. Since bismuth is present in the layer in advance, diffusion of bismuth from the capacitor film that occurs when the capacitor film is formed can be prevented by the diffusion preventing layer. As a result, it is possible to prevent the compositional deviation of the capacitor film caused by the bismuth from escaping from the capacitor film made of a ferroelectric material having a bismuth layered structure, thereby increasing the leakage current, deterioration of the breakdown voltage, film fatigue characteristics and imprint characteristics. It is possible to suppress deterioration of the characteristics of the capacitive element such as deterioration of the capacitor. Furthermore, since the diffusion preventing layer prevents bismuth from escaping from the capacitor film and also serves as a capacitor lower electrode, the structure of the capacitor element is simplified and the capacitor element can be easily formed. .

  In the first or second capacitor element manufacturing method, the diffusion prevention layer is preferably formed by a sputtering method in an oxygen atmosphere.

  In this way, a diffusion barrier film having a high barrier property that can prevent diffusion of bismuth from the capacitor film can be easily formed.

  According to a third method of manufacturing a capacitive element according to the present invention, a conductive metal oxide film and a bismuth oxide film are sequentially formed on a substrate by a step of heat treatment and a heat treatment. Interdiffusion between the conductive metal oxide film and the bismuth oxide film to form a diffusion prevention layer, and the bismuth oxide layer remaining on the diffusion prevention layer is removed. A step of forming a capacitor lower electrode on the diffusion prevention layer after removing the bismuth oxide layer; and a step of forming a capacitor film made of a ferroelectric material having a bismuth layer structure on the capacitor lower electrode. And a step of forming a capacitor upper electrode on the capacitor film.

  According to the third method of manufacturing a capacitor element, a diffusion prevention layer made of a material in which bismuth oxide is added to a conductive metal oxide is formed under the capacitor lower electrode, and bismuth exists in advance in the diffusion prevention layer. Therefore, diffusion of bismuth from the capacitor film that occurs when the capacitor film is formed can be prevented by the diffusion preventing layer. As a result, it is possible to prevent the compositional deviation of the capacitor film caused by the bismuth from escaping from the capacitor film made of a ferroelectric material having a bismuth layered structure, thereby increasing the leakage current, deterioration of the breakdown voltage, film fatigue characteristics and imprint characteristics. It is possible to suppress deterioration of the characteristics of the capacitive element such as deterioration of the capacitor. Furthermore, a diffusion barrier layer having a high barrier property that can prevent diffusion of bismuth from the capacitor film can be easily formed by an industrial method.

  According to a fourth method for manufacturing a capacitive element according to the present invention, a conductive metal oxide film and a bismuth oxide film are formed on a substrate by a step of sequentially forming a conductive metal oxide film and a bismuth oxide film, and heat treatment. Forming a lower capacitor electrode made of a diffusion preventing layer formed by mutual diffusion of a conductive metal oxide film and a bismuth oxide film, and remaining on the lower capacitor electrode A step of removing the bismuth oxide layer, a step of forming a capacitor film made of a ferroelectric having a bismuth layer structure on the capacitor lower electrode after removing the bismuth oxide layer, and a capacitor upper electrode on the capacitor film Forming the step.

  According to the fourth method for manufacturing a capacitor element, a capacitor lower electrode composed of a diffusion prevention layer made of a material in which bismuth oxide is added to a conductive metal oxide is formed under the capacitor film to prevent diffusion. Since bismuth is present in the layer in advance, diffusion of bismuth from the capacitor film that occurs when the capacitor film is formed can be prevented by the diffusion preventing layer. As a result, it is possible to prevent the compositional deviation of the capacitor film caused by the bismuth from escaping from the capacitor film made of a ferroelectric material having a bismuth layered structure, thereby increasing the leakage current, deterioration of the breakdown voltage, film fatigue characteristics and imprint characteristics. It is possible to suppress deterioration of the characteristics of the capacitive element such as deterioration of the capacitor. In addition, since the diffusion preventing layer prevents bismuth from escaping from the capacitor film and serves as a capacitor lower electrode, the structure of the capacitor element can be simplified and the capacitor element can be easily formed. . Furthermore, a diffusion barrier layer having a high barrier property that can prevent diffusion of bismuth from the capacitor film can be easily formed by an industrial method.

  In the third or fourth capacitor element manufacturing method, the step of removing the bismuth oxide layer is preferably performed using a chemical mechanical polishing method.

  Thus, the formation of the third or fourth capacitor element can be realized more easily by using an industrial method.

  According to the first capacitor element and the first capacitor element manufacturing method of the present invention, a diffusion prevention layer made of a material obtained by adding bismuth oxide to a conductive metal oxide is formed under the capacitor lower electrode, Since bismuth is present in the diffusion prevention layer in advance, diffusion of bismuth from the capacitance film that occurs during the formation of the capacitance film can be prevented by the diffusion prevention layer. As a result, it is possible to prevent the compositional deviation of the capacitor film caused by the bismuth from escaping from the capacitor film made of a ferroelectric material having a bismuth layered structure, thereby increasing the leakage current, deterioration of the breakdown voltage, film fatigue characteristics and imprint characteristics. It is possible to suppress deterioration of the characteristics of the capacitive element such as deterioration of the capacitor. In addition to these effects, according to the third method for manufacturing a capacitor element, a diffusion barrier layer having a high barrier property that can prevent diffusion of bismuth from the capacitor film can be easily formed by an industrial method.

  Further, according to the second capacitor element and the method of manufacturing the second capacitor element of the present invention, the diffusion prevention layer made of a material in which bismuth oxide is added to a conductive metal oxide is formed under the capacitor film. Since the capacitor lower electrode is formed and bismuth is present in the diffusion preventing layer in advance, the diffusion preventing layer can prevent the diffusion of bismuth from the capacitor film when the capacitor film is formed. As a result, it is possible to prevent the compositional deviation of the capacitor film caused by the bismuth from escaping from the capacitor film made of a ferroelectric material having a bismuth layered structure, thereby increasing the leakage current, deterioration of the breakdown voltage, film fatigue characteristics and imprint characteristics. It is possible to suppress deterioration of the characteristics of the capacitive element such as deterioration of the capacitor. Furthermore, since the diffusion preventing layer prevents bismuth from escaping from the capacitor film and also serves as a capacitor lower electrode, the structure of the capacitor element is simplified and the capacitor element can be easily formed. . In addition to these effects, according to the fourth method for manufacturing a capacitive element, a diffusion barrier layer having a high barrier property that can prevent diffusion of bismuth from the capacitive film can be easily formed by an industrial method.

  Hereinafter, embodiments of the present invention will be described with reference to the drawings.

(First embodiment)
The capacitive element according to the first embodiment of the present invention will be described below with reference to FIGS.

  FIG. 1 is a cross-sectional view of a structure when the capacitor according to the first embodiment of the present invention is stacked on a transistor.

  As shown in FIG. 1, the element formation region partitioned by the isolation insulating film 2 in the semiconductor support substrate 1 includes an impurity diffusion region 3 that is a source region or a drain region formed on the surface of the semiconductor support substrate 1 and the semiconductor support. A transistor 5 composed of a gate 4 formed on the substrate 1 is formed. On the semiconductor support substrate 1, a first interlayer film 6 (having a film thickness of about 500 nm) made of an oxide film added with B (boron) and P (phosphorus) is formed so as to cover the transistor 5. The first interlayer film 6 is provided with a contact plug 7 made of tungsten having a lower end connected to the impurity diffusion region 3.

On the first interlayer film 6, an oxygen diffusion prevention layer 8a whose lower surface is connected to the upper end of the contact plug 7 and a bismuth diffusion prevention layer 9a (film thickness is about 50 nm) are laminated in order from the bottom. A diffusion prevention layer 10a is formed. The oxygen diffusion preventing layer 8a has a structure in which TiAlN, Ir, and IrO ₂ are laminated in order from the bottom, and the film thicknesses are 50 nm, 50 nm, and 50 nm, respectively.

On the first interlayer film 6, a second interlayer film 11 (having a thickness of about 800 nm) made of an oxide film having an opening 11a reaching the bismuth diffusion layer 9a is formed. On the second interlayer film 11 including the opening 11a, a capacitor lower electrode 12 made of IrO ₂ having a film thickness of 25 nm is formed. The capacitor lower electrode 12 is electrically connected to the impurity diffusion region 3 of the transistor 5 through the diffusion prevention layer 10 a and the contact plug 7.

On the capacitor lower electrode 12, a ferroelectric film 13 as a capacitor film made of SBTN having a film thickness of 50 nm is formed. On the ferroelectric film 13, a capacitor upper electrode 14 made of IrO ₂ having a thickness of 50 nm is formed. The transistor 104 becomes an access transistor, and the capacitor 15 formed of the diffusion prevention layer 10a, the capacitor lower electrode 12, the ferroelectric film 13, and the capacitor upper electrode 14 becomes a data storage capacitor, thereby forming a nonvolatile memory. The

  FIG. 2 shows an enlarged cross-sectional view of the structure of the bismuth diffusion preventing layer 9a.

  As shown in FIG. 2, the bismuth diffusion preventing layer 9a has a polycrystalline structure, and bismuth oxide is precipitated at the grain boundaries 21a of the fine spherical crystal 20a having a particle diameter of about 10 nm. The crystal 20a is a rutile type crystal made of iridium and oxygen. The bismuth diffusion preventing layer 9a is represented, for example, by the following composition formula (1).

IrO ₂ + 0.1 BiO _2/3 (1)
Hereinafter, operations and effects obtained by adopting the above-described structure will be described with reference to FIGS. 3 (a) and 3 (b) and FIGS. 4 (a) and 4 (b).

  In general, the diffusion of atoms into a polycrystalline film occurs mainly through grain boundaries that serve as high-speed diffusion paths. FIGS. 3 (a) and 3 (b) and FIGS. 4 (a) and 4 (b) are diagrams for explaining the diffusion of atoms through the grain boundaries, and the grain boundaries in the diffusion preventing layer 10a and the capacitor lower electrode 12 are illustrated. The distribution of the mole fraction of bismuth with respect to all the metals in the depth [nm] direction is schematically shown. Specifically, FIGS. 3A and 3B show the formation of the ferroelectric film 13 in the case where the bismuth diffusion prevention layer 9a is not formed between the oxygen diffusion prevention layer 8a and the capacitor lower electrode 12. FIG. The relationship between the depth from the surface of the capacitor lower electrode 12 before ((a)) and after formation ((b)) and the mole fraction of bismuth with respect to all the metals in the grain boundaries is shown. 4A and 4B show bismuth between the oxygen diffusion prevention layer 8a and the capacitor lower electrode 12 before ((a)) and after ((b)) formation of the ferroelectric film 13. FIG. In the case where the diffusion preventing layer 9a is formed, the relationship between the depth from the surface of the capacitor lower electrode 12 and the mole fraction of bismuth with respect to all the metals in the grain boundary is shown.

  First, the case where the bismuth diffusion prevention layer 9a is not formed will be described with reference to FIGS. 3 (a) and 3 (b).

  As shown in FIG. 3 (a), before the ferroelectric film 13 is formed, the molar fraction of bismuth in the capacitor lower electrode 12 and the oxygen diffusion prevention layer 8a is zero (the solid line in FIG. 3 (a)). reference). Next, as shown in FIG. 3 (b), after the ferroelectric film 13 is formed, bismuth diffuses from the ferroelectric film 13 toward the capacitor lower electrode 12 (the solid line in FIG. 3 (b)). reference). Further, since the capacitor lower electrode 12 does not contain bismuth at the grain boundary, bismuth from the ferroelectric film 13 easily diffuses through the capacitor lower electrode 12 and reaches the oxygen diffusion preventing layer 8a.

  On the other hand, the case where the bismuth diffusion preventing layer 9a is formed will be described with reference to FIGS. 4 (a) and 4 (b).

  As shown in FIG. 4 (a), before the ferroelectric film 13 is formed, bismuth exists only in the bismuth diffusion preventing layer 9a (see the broken line in FIG. 4 (a)). Next, as shown in FIG. 4 (b), after the ferroelectric film 13 is formed, bismuth from the ferroelectric film 13 diffuses up to the capacitor lower electrode 12 (in FIG. 4 (b)). Since bismuth exists in advance in the bismuth diffusion prevention layer 9a (see the broken line in FIG. 4B), it is possible to suppress the diffusion of bismuth into the bismuth diffusion prevention layer 9a.

  Further, the bismuth diffusion prevention layer is formed by making the mole fraction of bismuth with respect to all metals contained in the bismuth diffusion prevention layer 9a larger than the mole fraction of bismuth with respect to all metals contained in the capacitor lower electrode 12. 9a and the lower electrode 12 of the capacitor have a gradient in the molar fraction of bismuth, so that the diffusion of bismuth from the capacitor film 13 during the formation of the capacitor film 13 can be more reliably prevented by the bismuth diffusion prevention layer 9a. .

  As described above, according to the capacitor according to the first embodiment, the bismuth diffusion prevention layer 9a is formed under the capacitor lower electrode 12, and bismuth is present in advance at the grain boundary of the bismuth diffusion prevention layer 9a. Therefore, the diffusion of bismuth from the capacitive film 13 that occurs when the capacitive film 13 is formed can be prevented by the bismuth diffusion preventing layer 9a. This prevents a composition shift of the capacitive film 13 caused by bismuth escaping from the capacitive film 13 made of a ferroelectric material having a bismuth layer structure, so that an increase in leakage current, deterioration of breakdown voltage, film fatigue characteristics, and It is possible to suppress deterioration of the characteristics of the capacitive element such as deterioration of print characteristics.

  In the present embodiment, iridium oxide crystals are used as the bismuth diffusion prevention layer 9a. For example, other platinum such as Pt, Ru, Pd, Rh, Os represented by the following composition formula (2) is used. It may be an oxide of a group metal.

MptO ₂ + x BiO _2/3 (2)
However, Mpt is a platinum group metal, and x satisfies the relationship of 0.05 <x <0.5.

  As described above, x may be in the range of 0.05 to 0.5. When x is 0.05 or less, bismuth is insufficient, so that bismuth loss in the ferroelectric film 13 is sufficiently suppressed. This is because, on the other hand, when x is 0.5 or more, the conductivity is rapidly decreased.

(Second Embodiment)
Hereinafter, a capacitive element according to a second embodiment of the present invention will be described with reference to FIGS.

  The structure of the capacitive element according to the second embodiment of the present invention is the same as that of the capacitive element according to the first embodiment shown in FIG. The capacitive element according to the second embodiment of the present invention differs from the capacitive element according to the first embodiment in that the material of the bismuth diffusion prevention layer 9b constituting the diffusion prevention layer 10b according to the second embodiment That is, the material of the bismuth diffusion prevention layer 9a constituting the diffusion prevention layer 10a according to the first embodiment is different.

  Therefore, the bismuth diffusion prevention layer 9b in the second embodiment will be specifically described below.

  The cross-sectional view in which the structure of the bismuth diffusion preventing layer 9b is enlarged is the same as FIG. 2 used in the first embodiment.

  As shown in FIG. 2, the bismuth diffusion preventing layer 9b has a polycrystalline structure, and bismuth oxide is precipitated at the grain boundaries 31a of the fine spherical crystal 30a having a particle diameter of about 10 nm. The crystal 30a is a perovskite crystal made of strontium, iridium, and oxygen. The bismuth diffusion preventing layer 9b is represented, for example, by the following composition formula (3).

SrIrO ₃ +0.2 BiO _2/3 (3)
Below, the effect | action and effect which are obtained by employ | adopting the above structure are demonstrated.

  In the first embodiment, although bismuth diffusion through the grain boundary 21a can be suppressed, the crystal 20a is made of iridium oxide that is energetically unstable. For example, as shown in the following reaction formula (4) Since iridium oxide and bismuth react with each other, bismuth is absorbed into the crystal 20a, so that the concentration of bismuth at the grain boundary 21a decreases. For this reason, it is not easy to completely suppress bismuth loss in the ferroelectric film 13.

2 IrO ₂ + Bi ₂ O ₃ → Bi ₂ Ir ₂ O ₇ (4)
However, in this embodiment, since the bismuth diffusion preventing layer 9b is made of an energetically stable perovskite crystal made of strontium, iridium, and oxygen, the reaction between the perovskite crystal and bismuth can be suppressed. The concentration of bismuth in does not decrease. For this reason, bismuth omission in the ferroelectric film 13 can be completely suppressed.

  In this embodiment, a perovskite crystal made of strontium, iridium, and oxygen is used as the bismuth diffusion prevention layer 9b. For example, another conductive perovskite crystal represented by the following composition formula (5) is used. May be.

MaMbO ₃ + 2x BiO _2/3 (5)
However, Ma is 1 or 2 or more types of metals chosen from 1, 2, or a trivalent metal, for example, Mg, Ca, Sr, Ba, Y, Bi, Pb, La, Ce, Pr, Nd, It is selected from Sm, Eu, Gd, Tb, Er, Tm, or Lu.

  Mb is a metal capable of 6-coordination. For example, Pt, Ir, Ru, Pd, Rh, Os, V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, Fe, Co, Ni Or Cu.

  Further, x satisfies the relational expression of 0.05 <x <0.5.

  As described above, x may be in the range of 0.05 to 0.5. When x is 0.05 or less, bismuth is insufficient, so that bismuth loss in the ferroelectric film 13 is sufficiently suppressed. This is because, on the other hand, when x is 0.5 or more, the conductivity is rapidly decreased.

(Third embodiment)
A capacitive element according to the third embodiment of the present invention will be described below with reference to FIGS.

  The structure of the capacitive element according to the third embodiment of the present invention is the same as that of the capacitive element according to the first embodiment shown in FIG. The capacitive element according to the third embodiment of the present invention differs from the capacitive element according to the first embodiment in that the material of the bismuth diffusion prevention layer 9c constituting the diffusion prevention layer 10c according to the third embodiment That is, the material of the bismuth diffusion prevention layer 9a constituting the diffusion prevention layer 10a according to the first embodiment is different.

  Therefore, the bismuth diffusion prevention layer 9c in the third embodiment will be specifically described below.

  The cross-sectional view in which the structure of the bismuth diffusion preventing layer 9c is enlarged is the same as FIG. 2 used in the first embodiment.

  As shown in FIG. 2, the bismuth diffusion preventing layer 9c has a polycrystalline structure, and bismuth oxide is precipitated at the grain boundaries 41a of the fine spherical crystals 40a having a grain size of about 10 nm. The crystal 40a is a pyrochlore type crystal made of bismuth, iridium, and oxygen. The bismuth diffusion preventing layer 9c is represented, for example, by the following composition formula (6).

Bi ₂ Ir ₂ O ₇ +0.4 BiO _2/3 (6)
Below, the effect | action and effect which are obtained by employ | adopting the above structure are demonstrated.

  In the first embodiment, although bismuth diffusion through the grain boundary 21a can be suppressed, the crystal 20a is made of iridium oxide that is energetically unstable. Therefore, as described in the second embodiment, iridium oxide and Since bismuth is absorbed in the crystal 20a due to the reaction with bismuth, it is not easy to completely prevent bismuth loss in the ferroelectric film 13.

  However, in this embodiment, since an energetically stable pyrochlore crystal made of bismuth, iridium, and oxygen is used as the bismuth diffusion preventing layer 9c, the reaction between the pyrochlore crystal and bismuth can be suppressed. The concentration of bismuth in the boundary 41a does not decrease. For this reason, bismuth omission in the ferroelectric film 13 can be completely suppressed.

The effect of suppressing bismuth loss in the ferroelectric film 13 is the same when the pyrochlore type crystal is used as the bismuth diffusion preventing layer 9c and when the perovskite type crystal is used as in the second embodiment. It is. However, since the chemical formula and the crystal structure are different between the perovskite type and the pyrochlore type, combinations of metals that can become Ma and Mb differ depending on the valence and ionic radius. For this reason, the combination of metals that can become Ma and Mb is preferably determined based on energy stability or conductivity. In consideration of actual manufacturing, it is preferable to use as much as possible the metal contained as a component of the ferroelectric film 13 or the capacitor lower electrode 12 for the combination of metals that can be Ma and Mb. This is because when a metal other than the metal contained as a component of the ferroelectric film 13 or the capacitor lower electrode 12 is used, the metal component contaminates the manufacturing facility, and the impurity component of the ferroelectric film 13 or the transistor 5 This is because there is a possibility of adverse effects. Therefore, for example, when SBTN is used as the ferroelectric film 13 and IrO ₂ is used as the capacitor lower electrode 12, Sr, Bi, and Ir components are included, so that SrIrO ₃ and Bi ₂ Ir ₂ O ₇ are replaced with bismuth. It may be used as a diffusion preventing layer. SrIrO ₃ is a perovskite type, and Bi ₂ Ir ₂ O ₇ is a pyrochlore type.

  In this embodiment, a pyrochlore type crystal composed of bismuth, iridium, and oxygen is used as the bismuth diffusion preventing layer 9c. For example, another conductive pyrochlore type crystal represented by the following composition formula (7) is used. May be.

Ma ₂ Mb ₂ O ₇ + 4x BiO _2/3 (7)
However, Ma is 1 or 2 or more types of metals chosen from 1, 2, or a trivalent metal, for example, Mg, Ca, Sr, Ba, Y, Bi, Pb, La, Ce, Pr, Nd, Sm , Eu, Gd, Tb, Er, Tm, or Lu.

  Mb is a metal capable of 6-coordination. For example, Pt, Ir, Ru, Pd, Rh, Os, V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, Fe, Co, Ni Or Cu.

  Further, x satisfies the relational expression of 0.05 <x <0.5.

  As described above, x may be in the range of 0.05 to 0.5. When x is 0.05 or less, bismuth becomes insufficient, so that bismuth omission in the ferroelectric film 13 is sufficiently suppressed. This is because, on the other hand, when x is 0.5 or more, the conductivity is rapidly decreased.

(Fourth embodiment)
Hereinafter, a method for manufacturing a capacitive element according to the fourth embodiment of the present invention will be described with reference to FIGS. 5 (a) to 5 (d).

  5A to 5D are process cross-sectional views illustrating a method for manufacturing a capacitor element stacked on a transistor.

  First, as shown in FIG. 5A, an element formation region partitioned by an isolation insulating film 2 formed on a semiconductor support substrate 1 is divided into an impurity diffusion region 3 serving as a source region or a drain region and a gate 4. The configured transistor 5 is formed. Next, a first interlayer film 6 (having a film thickness of about 500 nm) made of an oxide film to which B and P are added is formed on the semiconductor support substrate 1 so as to cover the transistor 5. A contact plug 7 made of tungsten is formed on one interlayer film 6.

Next, as shown in FIG. 5 (b), on the first interlayer film 6, an oxygen diffusion prevention layer 8a and a bismuth diffusion prevention layer 9a (thickness is about 50 mm) whose lower surface is connected to the upper end of the contact plug 7. nm) are stacked in order from the bottom. The oxygen diffusion preventing layer 8a has a structure in which TiAlN, Ir, and IrO ₂ are laminated in order from the lower layer, and the film thicknesses are 50 nm, 50 nm, and 50 nm, respectively. Next, the oxygen diffusion prevention layer 8a and the bismuth diffusion prevention layer 9a are processed into a predetermined shape to form the diffusion prevention layer 10a. A method for manufacturing the bismuth diffusion preventing layer 9a will be described in detail later.

Next, as shown in FIG. 5C, a second interlayer film 11 (thickness is about 800 nm) made of an oxide film is formed on the first interlayer film 6 so as to cover the diffusion prevention layer 10a. Then, an opening 11a is formed in the second interlayer film 11 to expose the bismuth diffusion preventing layer 9a. Next, the capacitor lower electrode 12 made of IrO ₂ having a thickness of 25 nm is formed on the second interlayer film 11 including the opening 11a. The capacitor lower electrode 12 is electrically connected to the impurity diffusion region 3 of the transistor 5 through the diffusion prevention layer 10 a and the contact plug 7.

Next, as shown in FIG. 5D, a ferroelectric film 13 made of SBTN having a film thickness of 50 nm is deposited on the capacitor lower electrode 12 by MOCVD (Metal Organic Chemical Vapor Deposition). . In this case, organic metals such as Sr, Bi, Ta, and Nb are used as source gases, and an inert gas Ar gas and an active gas oxygen gas are used on the semiconductor support substrate 1 maintained at 350 ° C. The amorphous ferroelectric film 13 can be formed by thermally decomposing the gas made of the organic metal. Next, a capacitor upper electrode 14 made of IrO ₂ having a thickness of 50 nm is formed on the ferroelectric film 13. Next, after forming the capacitor upper electrode 14, the ferroelectric film 13 is crystallized by heat treatment at 800 ° C. for 1 minute in an oxygen atmosphere by an RTA (Rapid Thermal Annealing) method. The transistor 5 becomes an access transistor, and the capacitor 15 including the diffusion prevention layer 10a, the capacitor lower electrode 12, the capacitor insulating film 13, and the capacitor upper electrode 14 becomes a data storage capacitor, thereby forming a nonvolatile memory. .

  Here, a manufacturing method of the bismuth diffusion preventing layer 9a will be described.

  The bismuth diffusion preventing layer 9a is formed using a sputtering method. Specifically, an alloy of iridium and bismuth is used as a target, the composition ratio of iridium and bismuth is preferably 1: 0.05 to 0.5, and the more preferable composition ratio of iridium and bismuth is 1: 0.1. As a gas used for the sputtering method, an inert gas Ar gas and an active gas oxygen gas are used. The semiconductor support substrate 1 is kept at 100 ° C. or lower and preferably at room temperature. By holding the semiconductor support substrate 1 at room temperature, fine iridium oxide spherical crystals having a particle size of about 10 nm are formed, and bismuth oxide is precipitated at the crystal grain boundaries. After the film formation, the crystal is densified by heat treatment at 650 ° C. for 1 minute in an oxygen atmosphere by the RTA method. The heat treatment temperature is preferably 400 ° C. or higher at which crystal densification occurs and 800 ° C. or lower at which hillock generation or reduction does not occur. By the sputtering method performed under such conditions, it is possible to form the bismuth diffusion preventing layer 9a having a high barrier property that can suppress the diffusion of bismuth.

  In the present embodiment, the case where the bismuth diffusion prevention layer 9a made of the iridium oxide film in which bismuth oxide is precipitated at the grain boundary is formed by the sputtering method has been described. However, the second embodiment is performed instead of the iridium oxide film. The conductive perovskite type metal oxide 9b described in the embodiment, the conductive pyrochlore type metal oxide 9c described in the third embodiment, another platinum group metal oxide, or another conductive metal oxide may be used. Good.

First, the case where the bismuth diffusion prevention layer 9b made of a conductive perovskite metal oxide is formed by sputtering will be described. Here, as an example, the case where the conductive perovskite metal oxide is SrIrO ₃ will be described.

Specifically, an alloy of iridium, strontium, and bismuth is used as the target, and the composition ratio of iridium, strontium, and bismuth is preferably 1: 1: 0.1 to 1, and iridium, strontium, and bismuth. The more preferable composition ratio is about 1: 1: 0.2. As gases used for sputtering, an Ar gas as an inert gas and an oxygen gas as an active gas are used. The semiconductor support substrate 1 is kept at 100 ° C. or lower and preferably at room temperature. By holding the semiconductor support substrate 1 at room temperature, fine SrIrO ₃ spherical crystals having a particle size of about 10 nm are formed, and bismuth oxide is precipitated at the crystal grain boundaries. After the film formation, the crystal is densified by heat treatment at 650 ° C. for 1 minute in an oxygen atmosphere by the RTA method. The heat treatment temperature is preferably 400 ° C. or higher where crystal densification occurs and 800 ° C. or lower where hillock generation or reduction does not occur.

Next, the case where the bismuth diffusion prevention layer 9c made of a conductive pyrochlore type metal oxide is formed by sputtering will be described. Here, as an example, a case where the conductive pyrochlore type metal oxide is Bi ₂ Ir ₂ O ₇ will be described.

Specifically, an alloy of iridium and bismuth is used as a target, and the composition ratio of iridium and bismuth is preferably 1: 1.1 to 2, and a more preferable composition ratio of iridium and bismuth is 1: 1.2. As gases used for sputtering, an Ar gas as an inert gas and an oxygen gas as an active gas are used. The semiconductor support substrate 1 is kept at 100 ° C. or lower and preferably at room temperature. By holding the semiconductor substrate 1 at room temperature, fine Bi ₂ Ir ₂ O ₇ spherical crystals with a particle size of about 10 nm are formed, and excess bismuth oxide is precipitated at the crystal grain boundaries. After film formation, the crystal is densified by heat treatment in an oxygen atmosphere for 1 minute by the RTA method. The heat treatment temperature is preferably 400 ° C. or higher at which crystal densification occurs and 800 ° C. or lower at which hillock generation or reduction does not occur.

  In this embodiment, the sputtering method is used as a method for forming the bismuth diffusion preventing layers 9a, 9b, and 9c. However, a solution coating method using an organometallic solution may be used, or an organometallic gas may be used. The MOCVD method used may be used.

(Fifth embodiment)
Hereinafter, a method for manufacturing a capacitive element according to the fifth embodiment of the present invention will be described with reference to FIGS. 5 (a) to 5 (d).

  Since the manufacturing method of the capacitive element according to the fifth embodiment differs from the manufacturing method of the capacitive element according to the fourth embodiment as described later, the manufacturing method of the bismuth diffusion prevention layer 9a is different. A method for producing the bismuth diffusion preventing layer 9a will be described.

  After forming a bismuth oxide layer having a film thickness of 30 nm on the iridium oxide layer serving as the oxygen diffusion preventing layer 8a (see FIG. 5 (b)), the RTA method is used for 1 minute at 650 ° C. in an oxygen atmosphere. Heat treatment is performed. Therefore, at the interface between the iridium oxide layer and the bismuth oxide layer, mutual diffusion occurs by heat treatment, so that a bismuth diffusion prevention layer 9a in which bismuth oxide is mixed with iridium oxide is formed with a thickness of 20 nm. Next, the excess bismuth oxide layer remaining on the bismuth diffusion preventing layer 9a is removed by a CMP (Chemical Mechanical Polishing) method. In this way, the bismuth diffusion preventing layer 9a can be easily formed industrially.

In the first to fifth embodiments, the case where the oxygen diffusion prevention layer 8a is a multilayer film composed of TiAlN, Ir, and IrO ₂ has been described. However, the oxygen diffusion prevention layer 8a has a different structure. It may be the case. For example, since the bismuth diffusion prevention layer 9a also plays the role of IrO ₂ constituting the oxygen diffusion prevention layer 8a, the oxygen diffusion prevention layer 8a may be a multilayer film composed simply of TiAlN and Ir.

In the first to fifth embodiments, IrO ₂ is used as the capacitor lower electrode 12, but other platinum group metals such as Pt, platinum group metal oxides, or the like may be used to prevent bismuth diffusion. The same material as the layer 9a, 9b or 9c may be used. Here, FIG. 6 is a structural cross-sectional view of the capacitive element according to the fifth embodiment stacked on a transistor, and shows a modification of each of the above-described embodiments. When the same material as the bismuth diffusion preventing layer 9a, 9b or 9c is used as the capacitor lower electrode 12, the bismuth diffusion preventing layer 9a, 9b or 9c is not formed as shown in FIG. The capacitor lower electrode 12 made of the same material as 9a, 9b or 9c can also be formed directly on the first interlayer film 6. In this case, as described in the first embodiment, bismuth is present in the grain boundary of the bismuth diffusion preventing layer 9a (9b or 9c), so that bismuth in the capacitive film 13 is converted into the bismuth diffusion preventing layer 9a. (9b or 9c) can be prevented from diffusing. Furthermore, by making the mole fraction of bismuth with respect to all metals contained in the bismuth diffusion prevention layer 9a (9b or 9c) larger than the mole fraction of bismuth with respect to all metals contained in the capacitive film 13, Since the concentration gradient of bismuth in the bismuth diffusion preventing layer 9a (9b or 9c) is higher than the concentration gradient of bismuth in the capacitance film 13, the diffusion of bismuth from the capacitance film 13 that occurs during the formation of the capacitance film 13 is bismuth diffusion. It can prevent more reliably by the prevention layer 9a (9b or 9c).

  In the first to fifth embodiments, the case where the ferroelectric film 13 is made of SBTN has been described. However, other bismuth layered structure ferroelectric films such as BLT may be used.

  In the first to fifth embodiments, the diffusion preventing layer 10a, 10b or 10c has been described as being processed into the same shape, but the oxygen diffusion preventing layer 8a constituting the diffusion preventing layer 10a, 10b or 10c. And the bismuth diffusion preventing layer 9a, 9b or 9c may be processed into independent shapes.

  In the first to fifth embodiments, when the capacitive element 15 has a three-dimensional stack type structure formed in the concave opening 11 a in order to increase the surface area of the ferroelectric film 12. However, as shown in FIG. 7, the capacitive element 15 has a planar stack type structure in which the ferroelectric film 12 is formed on a flat portion. Also good.

Further, when hydrogen diffusion into the capacitive element 15 becomes a problem, the surroundings of the capacitive element 15 according to the first to fifth embodiments are made to be SiN, SiON, Al ₂ O ₃ , TiAlO, TaAlO, TiSiO, Of course, it is possible to have a structure surrounded by a hydrogen barrier film containing one or more materials selected from TaSiO, TiAlN, TiAlON, TiSiN, TiSiON, TaAlN, TaAlON, TaSiN, TaSiON, Ti or Ta. . Thereby, the diffusion of hydrogen into the capacitive element 15 can be prevented, and the characteristic deterioration of the capacitive element can be prevented.

  As described above, according to the present invention, it is possible to prevent bismuth from escaping from the bismuth layered ferroelectric film by forming the bismuth diffusion preventing layer. Therefore, the capacitive element according to the present invention and the method for manufacturing the capacitive element It is useful to apply to a capacitive element using a bismuth layered structure ferroelectric.

FIG. 4 is a structural cross-sectional view showing a capacitive element according to first to third embodiments of the present invention stacked on a transistor. It is the structure sectional view in which the bismuth diffusion prevention layer in the capacity element concerning the 1st-the 3rd embodiment of the present invention was expanded. (a) and (b) are relationship diagrams between the bismuth concentration in the grain boundary and the depth from the surface of the capacitor lower electrode when the bismuth diffusion layer is not formed. (a) And (b) is a relationship figure of the bismuth density | concentration in a grain boundary in the case of forming a bismuth diffusion layer, and the depth from the capacity | capacitance lower electrode surface. (a)-(d) is process sectional drawing which shows the manufacturing method of the capacitive element which concerns on the 4th and 5th embodiment of this invention laminated | stacked on the transistor. It is a structure sectional view of the capacitive element concerning the modification of the 1st-a 5th embodiment of the present invention laminated on the transistor. It is process sectional drawing explaining the capacitive element which concerns on the modification of embodiment of this invention laminated | stacked on the transistor.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Semiconductor support substrate 2 Isolation insulating film 3 Impurity diffusion area | region 4 Gate 5 Transistor 6 1st interlayer film 7 Contact plug 8a Oxygen diffusion prevention layer 9a, 9b, 9c Bismuth diffusion prevention layer 10a, 10b, 10c Diffusion prevention layer 11 2nd Interlayer film 11a Opening 12 Capacitor lower electrode 13 Ferroelectric film 14 Capacitor upper electrode 15 Capacitance elements 20a, 30a, 40a Spherical crystals 21a, 31a, 41a Grain boundaries

Claims (17)

An anti-diffusion layer;
A capacitor lower electrode formed on the diffusion barrier layer;
A capacitor film made of a ferroelectric material having a bismuth layer structure formed on the capacitor lower electrode;
A capacitor upper electrode formed on the capacitor film;
The diffusion prevention layer is made of a material obtained by adding bismuth oxide to a conductive metal oxide.   The mole fraction of bismuth with respect to all metals contained in the diffusion barrier layer is larger than the mole fraction of bismuth with respect to all metals contained in the capacitor lower electrode. Capacitance element. A capacitor lower electrode comprising a diffusion barrier layer;
A capacitor film made of a ferroelectric material having a bismuth layer structure formed on the capacitor lower electrode;
A capacitor upper electrode formed on the capacitor film;
The diffusion prevention layer is made of a material obtained by adding bismuth oxide to a conductive metal oxide.   4. The capacitor according to claim 3, wherein a mole fraction of bismuth with respect to all metals contained in the diffusion preventing layer is larger than a mole fraction of bismuth with respect to all metals contained in the capacitor film. element. The diffusion prevention layer has a polycrystalline structure of the conductive metal oxide,
The capacitive element according to claim 1, wherein the bismuth oxide is precipitated at a grain boundary of the polycrystalline structure.   The capacitive element according to claim 1, wherein the conductive metal oxide is an oxide of a platinum group metal. The diffusion preventing layer has the following composition formula: MptO ₂ + x · BiO _2/3
(However, Mpt is a platinum group metal, and x satisfies the relational expression of 0.05 <x <0.5.)
The capacitor element according to claim 6, represented by:   The capacitive element according to claim 1, wherein the conductive metal oxide is a conductive perovskite oxide. The diffusion preventing layer has the following composition formula: MaMbO ₃ + 2 · x · BiO _2/3
(However, Ma is one or more metals selected from monovalent, divalent or trivalent metals, Mb is a metal capable of 6 coordination, and x is 0.05 <x <0.5. Is satisfied)
The capacitor element according to claim 8, wherein:   The capacitive element according to claim 1, wherein the conductive metal oxide is a conductive pyrochlore oxide. The diffusion preventing layer has the following composition formula: Ma ₂ Mb ₂ O ₇ + 4 · x · BiO _2/3
(However, Ma is one or more metals selected from monovalent, divalent or trivalent metals, Mb is a metal capable of 6 coordination, and x is 0.05 <x <0.5. Is satisfied)
The capacitor element according to claim 10, represented by: Forming a diffusion preventing layer made of a material obtained by adding bismuth oxide to a conductive metal oxide on a substrate;
Forming a capacitor lower electrode on the diffusion preventing layer;
Forming a capacitor film made of a ferroelectric material having a bismuth layer structure on the capacitor lower electrode;
And a step of forming a capacitor upper electrode on the capacitor film. Forming a capacitor lower electrode comprising a diffusion prevention layer made of a material obtained by adding bismuth oxide to a conductive metal oxide on a substrate;
Forming a capacitor film made of a ferroelectric material having a bismuth layer structure on the capacitor lower electrode;
And a step of forming a capacitor upper electrode on the capacitor film.   The method for manufacturing a capacitive element according to claim 12, wherein the diffusion prevention layer is formed by a sputtering method in an oxygen atmosphere. A step of sequentially forming a conductive metal oxide film and a bismuth oxide film on the substrate;
A step of causing a mutual diffusion between the conductive metal oxide film and the bismuth oxide film by a heat treatment to form a diffusion preventing layer formed by the mutual diffusion of the conductive metal oxide film and the bismuth oxide film. When,
Removing the bismuth oxide layer remaining on the diffusion preventing layer;
Forming a capacitor lower electrode on the diffusion barrier layer after removing the bismuth oxide layer;
Forming a capacitor film made of a ferroelectric material having a bismuth layer structure on the capacitor lower electrode;
And a step of forming a capacitor upper electrode on the capacitor film. A step of sequentially forming a conductive metal oxide film and a bismuth oxide film on the substrate;
The lower part of the capacitor is formed of a diffusion prevention layer formed by causing mutual diffusion between the conductive metal oxide film and the bismuth oxide film by heat treatment and mutual diffusion of the conductive metal oxide film and the bismuth oxide film. Forming an electrode;
Removing the bismuth oxide layer remaining on the capacitor lower electrode;
Forming a capacitor film made of a ferroelectric having a bismuth layer structure on the capacitor lower electrode after removing the bismuth oxide layer;
And a step of forming a capacitor upper electrode on the capacitor film.   The method for manufacturing a capacitive element according to claim 15, wherein the step of removing the bismuth oxide layer is performed using a chemical mechanical polishing method.

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