JP4676694B2 - Multilayer structure, semiconductor device and manufacturing method thereof - Google Patents

Description

  The present invention relates to a semiconductor device and a manufacturing method thereof, and more particularly, to a laminated structure constituting a multilayer wiring, a semiconductor device, and a manufacturing method thereof.

  With the recent high integration and miniaturization of semiconductor elements, semiconductor devices using an insulating film having a dielectric constant lower than that of a silicon oxide film as a wiring interlayer insulating film (hereinafter referred to as an interlayer insulating film) have been developed. Yes. For example, an interlayer insulating film in which a part of oxygen atoms contained in a silicon oxide film is replaced with fluorine or a chemical species containing at least carbon, or an interlayer in which fine vacancies are provided to achieve a low dielectric constant. Insulating films have been developed.

  However, many of the low dielectric constant interlayer insulating films have a problem that the adhesion between the interlayer insulating film and its upper and lower layers is weak due to the presence of chemical species including carbon on the surface in addition to the low density. is there.

  As a problem due to the lack of adhesion, first, a chemical mechanical polishing process (CMP: planarization process performed when forming embedded wiring), which is an essential process in recent semiconductor device manufacturing processes, is executed. There is a problem that peeling of the film occurs due to stress generated at the time, and wiring formation becomes difficult. Second, with the miniaturization of transistors, the number of transistors mounted on a chip increases, and the number of wirings inevitably increases. However, in order to meet the demand for chip size reduction, it is necessary to increase the number of wiring layers There is a problem of becoming. When the wiring part has a multi-layer structure, stress concentration at the interface increases, so if the adhesion at the contact interface between the interlayer insulating film and the adjacent film is not sufficient, film peeling occurs at the contact interface, As a result, the electrical reliability of the semiconductor device is lowered.

  Furthermore, since the semiconductor device undergoes processes such as dicing, packaging, and wire bonding in its assembly process, in particular, insufficient adhesion at the contact interface between the interlayer insulating film and the underlying substrate located thereunder, or the assembly process However, due to a dynamic load applied to the semiconductor device, film peeling occurs at the contact interface between the interlayer insulating film and the base substrate, and there is a problem that the electrical reliability of the semiconductor device is lowered.

  In order to solve such a problem, for example, Patent Document 1 discloses that an interlayer insulating film material is formed on a base substrate by applying plasma to the base substrate to make the base substrate surface hydrophilic. The manufacturing method of improving the adhesiveness is described.

  Further, in the conventional method for manufacturing a semiconductor device described in Patent Document 2, a dangling bond is formed on the surface of the base substrate by applying a physical impact called reverse sputtering to the base substrate, and is formed thereon. A manufacturing method for improving the adhesion with the interlayer insulating film is described. Similarly, in Patent Document 2, as a method for improving adhesion, as shown in FIG. 15, a silicon-rich inorganic material is interposed between an interlayer insulating film (organic dielectric film 29) and a base substrate (substrate 31 to be processed). A method of inserting a dielectric layer (adhesion layer) 30 is described.

Next, as a method for forming an interlayer insulating film, Patent Document 3 describes the purpose of promoting film densification and ring-opening polymerization after a film-forming composition composed of a polysilane compound or the like is applied to a substrate. A method of forming an interlayer insulating film by performing light and / or heat treatment in a non-oxidizing atmosphere is described.
JP 2003-115485 A (page 3) JP 2000-183052 A (Page 3-5) JP 2003-133306 A (page 3-6)

  However, the prior art described in Patent Document 1 has several problems when an insulator containing carbon atoms is used as a base substrate.

  The first problem is that by irradiating the base substrate with plasma, carbon is separated from the base substrate, and the relative dielectric constant of the base substrate is increased. As a result, the effective dielectric constant of the semiconductor device increases.

  A second problem is that the material used for the interlayer insulating film of the semiconductor device in the forming method is limited to a film formed by a coating method. As an effect of the manufacturing method described in Patent Document 1, as a result of making the surface of the base substrate hydrophilic, adhesion is improved by improving wettability when applying a coating material for forming an interlayer insulating film. To do. On the other hand, when a film deposited by chemical vapor deposition (hereinafter referred to as a CVD method) is used as an interlayer insulating film, the method described in Patent Document 1 uses an interlayer insulating film and a base substrate. In some cases, the effect of improving the adhesion cannot be obtained, or on the contrary.

  The third problem is that the vicinity of the base surface after plasma irradiation is reduced in density. The plasma irradiation to the base substrate is effective in improving the wettability of the coating solution, but there exists a low density interface where the composition has abruptly changed between the interlayer insulating film and the base substrate. Such a low-density interface layer becomes the starting point of film peeling, so that sufficient adhesion sufficient to ensure reliability cannot be obtained, and the dynamics that the semiconductor device undergoes during assembly processes such as dicing and wire bonding There is a problem that it does not reach a degree of adhesion that can withstand a dynamic load.

  As a fourth problem, there is a problem that the moisture absorption of the base substrate is improved by separating the carbon on the surface of the base substrate by plasma irradiation and imparting hydrophilicity. The relative dielectric constant of water is about 80, which is very high compared to the relative dielectric constant (generally 5.0 or less) of the interlayer insulating film used in semiconductor devices, so the base substrate absorbs water. However, if water is adsorbed on the surface, the relative dielectric constant of the base substrate increases, and consequently the effective dielectric constant of the semiconductor device significantly increases. In addition, after the semiconductor device is formed, depending on the use situation, water absorption occurs from the contact interface between the interlayer insulating film with few hydrophobic groups and the base substrate, and the effective dielectric constant is increased. In addition, the leakage current is increased and the time is increased. This causes a decrease in the lifetime of time-dependent dielectric breakdown (TDDB), and as a result, the electrical reliability of the semiconductor device deteriorates.

  Next, the conventional method for manufacturing a semiconductor device described in Patent Document 2 has the following problems when an insulator containing silicon and carbon is used as a base substrate. The first problem is that a layer in which an element such as carbon is released by applying a physical impact to generate a dangling bond becomes a silicon-rich layer in composition. Due to the presence of this silicon-rich layer, the effective relative dielectric constant increases, and when a metal wiring is formed later, there is a problem that the silicon-rich layer becomes a conduction path for the leakage current between the wirings. In the structure shown in FIG. 15 also described in Patent Document 2, a silicon-rich inorganic dielectric layer 30 (adhesion) is provided between an interlayer insulating film (organic dielectric film) 29 and a base substrate (substrate to be processed) 31. However, since the adhesion layer has a higher dielectric constant than the interlayer insulating film 29, the effective dielectric constant of the semiconductor device increases as a result. is there.

Next, in the manufacturing method described in Patent Document 3, after a coating film for forming an interlayer insulating film is formed on a base substrate, light irradiation is performed in a non-oxidizing atmosphere. The constituent elements of the contact interface do not change. Therefore, an interface having different constituent elements or an interface in which the composition ratio of the constituent elements changes abruptly exists between the interlayer insulating film and the base substrate. Therefore, the interlayer is formed by a generally used film forming method (such as thermal firing). Compared with the case where an insulating film is formed, there is a problem that the adhesion between the interlayer insulating film and the base substrate cannot be significantly improved.
In the method for forming an interlayer insulating film described in Patent Document 3, a silicon substrate is used as a base substrate. Even if light irradiation is performed after forming a coating film on the silicon substrate by the forming method, the composition ratio of the constituent elements on the surface of the silicon substrate does not change. Therefore, the main reason that the adhesion can be improved by the formation method is mainly the improvement of the cross-linking density of the interlayer insulating film by light irradiation. In this case, compared with the case where the interlayer insulating film is formed by thermal firing. Therefore, it is difficult to significantly improve the adhesion.

  When actually forming a multilayer wiring structure, an insulating film made of an element such as Si, O, C, N, or H is usually deposited under the interlayer insulating film. More specifically, the insulating film is often a cap film for preventing diffusion of copper, which is a wiring material formed in a lower layer, or an alloy containing copper as a main component. Examples of the constituent element of the cap film include Si, C, and N. In many cases, the cap film does not contain oxygen or contains only a trace amount of oxygen. An interlayer insulating film is formed on the cap film by the method described in Patent Document 3, and the interlayer insulating film and the base substrate are separated by a Si-Si bond cleavage and recombination reaction or ring-opening polymerization. Even if chemical bonds are generated, most of the generated chemical bonds are bonds such as silicon and carbon or silicon and nitrogen.

  Since the bond energy between silicon and carbon and the bond energy between silicon and nitrogen are lower than the bond energy between silicon and oxygen, for example, from the viewpoint of chemical bonding, the formation method allows the interlayer insulating film and the underlying layer to be bonded. It is difficult to achieve high adhesion with the insulating film.

  Thus, conventionally, when applied as an interlayer insulating film of a semiconductor device, the layers can be formed without increasing the effective dielectric constant of the semiconductor device and without degrading the performance of the film adjacent to the interlayer insulating film. A laminated structure showing high adhesion, a semiconductor device using the same, and a manufacturing method thereof have not been provided.

  The present invention has been made in view of such a problem, and when applied as an interlayer insulating film of a semiconductor device, the performance of a film adjacent to the interlayer insulating film is deteriorated without increasing the effective dielectric constant of the semiconductor device. An object of the present invention is to provide a laminated structure in which the layers show high adhesion, and a semiconductor device using the same and a method for manufacturing the same.

To achieve the above object, the present invention provides, in a first aspect, the interface of each of which contains at least silicon, the first and second insulating film formed to overlap a front Stories second insulating film a first transition layer formed, before SL and a second transition layer formed at the interface between the first insulating film, and included in common in the first and second transition layer The content ratio of at least one kind of element is different between the first insulating film in the first transition layer and the second insulating film in the second transition layer , respectively. Provide the body. In the above configuration, the thickness of the first transition layer is 70% or less of the thickness of the first insulating film before the formation of the first transition layer, and the thickness of the second transition layer is The thickness is preferably 70% or less of the thickness of the second insulating film before the formation of the second transition layer.

In order to achieve the above object, the present invention provides, as a second aspect, a first insulating film containing at least silicon, and a coating film containing at least silicon and applied on the first insulating film. A first transition layer formed at the interface between the second insulating film formed by baking the first insulating film and the second insulating film by altering a part of the first insulating film; and a second transition layer formed at the interface between the first insulating film by alteration of the part of the previous the coating film, and common to the first and second transition layer the content of at least one element contained, stacked above the first transition layer, wherein said first insulating film, and said second of said second insulating film in the transition layer, different from each A structure is provided. In the above configuration, the thickness of the first transition layer is 70% or less of the thickness of the first insulating film before the formation of the first transition layer, and the thickness of the second transition layer is It is preferably 70% or less of the film thickness of the coating film before forming the second transition layer.

In the first or second aspect of the present invention, each of the first and second transition layers contains oxygen atoms, and the first transition layer contains oxygen atoms more than the first insulating film. high content of the second transition layer is not preferable content of oxygen atoms is higher than the second insulating film.

In order to achieve the above object, the present invention provides, as a third aspect, a laminated structure having the structure according to any one of the first aspect and the second aspect of the present invention, which contains at least silicon. The third insulating film formed on the second insulating film and the third insulating film formed at the interface between the third insulating film by altering a part of the second insulating film. and of the transition layer, and a fourth transition layer formed at the interface between the second insulating film by alteration of the portion of the third insulating film, further comprising a second and third The content of at least one element contained in common in the transition layers of the third transition layer is the second insulating film in the third transition layer, and the third insulating film in the fourth transition layer , respectively. The present invention provides a laminated structure characterized by being different. In this configuration, the third and fourth transition layers each contain oxygen atoms, the third transition layer has a higher oxygen atom content than the second insulating film, and the fourth transition layer has the second transition layer. 3 it is not preferable content of oxygen atoms is higher than that of the insulating film.

  In any configuration of the third aspect of the present invention, the thickness of the third transition layer is 70% or less of the thickness of the second insulating film before the formation of the third transition layer. The thickness of the transition layer 4 is preferably 70% or less of the thickness of the third insulating film before the formation of the fourth transition layer.

In order to achieve the above object, according to a fourth aspect of the present invention, there is provided a laminated structure having the structure according to any one of the third aspect of the present invention, which is formed on the third insulating film. And at the interface between the concave portion reaching the second insulating film, the fourth insulating film containing at least silicon and formed on the inner surface of the concave portion, and the fourth insulating film of the second insulating film. a fifth transition layer formed, further comprising a transition layer of a 6 formed at the interface between the second insulating film of the fourth insulating film, a transition of the fifth and sixth content of at least one element contained in common layers, and the fifth said second insulating film in the transition layer, and the sixth said fourth insulating film in the transition layer, can vary respectively The laminated structure characterized by the above is provided. In this configuration, the fifth and sixth transition layers each contain oxygen atoms, the fifth transition layer has a higher oxygen atom content than the third insulating film, and the sixth transition layer has the first transition layer. 4 it is not preferable content of oxygen atoms is higher than that of the insulating film.

  In any configuration of the fourth aspect of the present invention, the thickness of the fifth transition layer is 70% or less of the thickness of the second insulating film before the formation of the fifth transition layer. The thickness of the transition layer 6 is preferably 70% or less of the thickness of the fourth insulating film before the sixth transition layer is formed.

  In any configuration of the first to fourth aspects of the present invention, it is preferable that the relative dielectric constant of the second insulating film is lower than that of the silicon oxide film. Moreover, it is preferable to have a fine hole inside the second insulating film.

  In order to achieve the above object, as a fifth aspect of the present invention, a multilayer structure wiring is formed in the laminated structure having any one of the first to fourth aspects of the present invention, and the wiring A semiconductor device is provided in which a transistor is mounted.

In order to achieve the above object, according to a sixth aspect of the present invention, there is provided a method for manufacturing a semiconductor device having a transistor mounted on a multi-layer wiring, wherein the first insulating film contains at least silicon. at least a step of forming a second insulating film containing at least silicon, the step of irradiating at least one ultraviolet to the first and second insulating film in an atmosphere containing oxygen, the above The present invention provides a method for manufacturing a semiconductor device.

In order to achieve the above object, according to a seventh aspect of the present invention, there is provided a method for manufacturing a semiconductor device having a transistor mounted on a multi-layer wiring, wherein the first insulating film contains at least silicon. irradiating at least a step of forming a coating film containing silicon, an ultraviolet to the first insulating film and the coating film in an atmosphere containing oxygen on a step of firing the coating film A method for manufacturing a semiconductor device is provided.

In order to achieve the above object, according to an eighth aspect of the present invention, there is provided a method of manufacturing a semiconductor device having a transistor mounted on a multi-layer wiring, wherein the first insulating film contains at least silicon. A step of forming a second insulating film containing at least silicon thereon, a step of forming a third insulating film containing at least silicon on the second insulating film, and the atmosphere containing oxygen And a step of irradiating the first, second, and third insulating films with ultraviolet rays . A method of manufacturing a semiconductor device is provided.

In order to achieve the above object, according to a ninth aspect of the present invention , there is provided a method for manufacturing a semiconductor device having a transistor mounted on a multi-layer wiring, wherein the silicon substrate contains at least silicon. Forming a first insulating film; forming a second insulating film containing at least silicon on the first insulating film; and a third containing at least silicon on the second insulating film. Forming an insulating film; forming an opening penetrating the third insulating film to reach the second insulating film; and forming a fourth insulating film containing at least silicon on the inner surface of the opening. A semiconductor device comprising: a step of forming; and a step of irradiating the substrate and the first, second, third, and fourth insulating films with ultraviolet light in an oxygen-containing atmosphere. Manufacturing of It is intended to provide the law.

[Features of the invention]
As a result of intensive studies to solve the above problems, the present inventor has a composition or composition ratio of the first insulating film containing at least Si and the second insulating film containing at least Si. It has been found that forming a transition layer in each of the first and second insulating films across the contact interface with the insulating film is effective in solving the above problem.

  The transition layer is characterized in that a first transition layer is formed on the first insulating film, and a second transition layer is formed on the second insulating film. Further, the composition ratio of at least one common element in the first transition layer, the second transition layer, and the contact interface is different from each of the first and second insulating films.

  More specifically, the composition ratio of the oxygen element is larger in the contact interface and in the first and second transition layers than in the first and second insulating films.

  In addition, in the method for manufacturing an insulating film structure according to the present invention, the film stack structure including the first insulating film and the second insulating film is irradiated with ultraviolet rays in an oxygen-containing atmosphere. The composition of the interface between the first insulating film and the second insulating film adjacent thereto is chemically modulated to form a transition layer in each of the first and second insulating films.

  In addition, in the method of manufacturing a semiconductor device according to the present invention, an atmosphere containing oxygen is formed after the composition for forming the second insulating film is deposited on the first insulating film until the formation of the buried wiring structure is completed. The method includes the step of irradiating the substrate with ultraviolet rays at least once.

[Action]
According to the present invention, the adhesion between the first insulating film and the second insulating film can be strengthened by the presence of the first and second transition layers having similar compositions. Further, oxygen atoms exist in the first and second transition layers, and the adhesion between the first insulating film and the second insulating film can be strengthened by the oxygen atoms. That is, since the bond energy between silicon and oxygen is higher than the bond energy between silicon and carbon and the bond energy between silicon and nitrogen, the presence of the transition layer causes the first insulating film and the second insulating film to bond with each other. Firmly adheres to the film.

  Further, even when a film that does not contain oxygen or has a small oxygen content is used as a film adjacent to the interlayer insulating film, adhesion with the interlayer insulating film can be improved. According to the present invention, the effective dielectric constant of the semiconductor device is kept low because the properties, relative dielectric constant, insulation resistance, moisture absorption resistance, etc. required for the insulating film used in the semiconductor device are not deteriorated. At the same time, the occurrence of leakage current can be prevented, and the adhesion between the interlayer insulating film and the adjacent film can be enhanced. Therefore, since the resistance to a mechanical load can be improved without degrading the performance of the semiconductor device, it is possible to realize high performance and high reliability of the semiconductor device.

If the laminated structure according to the present invention is applied to a semiconductor device,
(1) The resistance of the film stack structure to a mechanical load can be increased, and as a result, the reliability of the semiconductor device is improved.
(2) The increase in the relative dielectric constant of the base substrate can be suppressed to a lower level than when a known adhesion enhancing technique is applied, and the amount of increase in the relative dielectric constant can also be reduced as a film laminated structure electric body.
(3) Since the performance of the interlayer insulating film and the interlayer insulating film, such as electrical characteristics and hygroscopicity, is not deteriorated, an increase in leakage current can be suppressed and a semiconductor device realizing low leakage current can be obtained.
The effect is obtained.

  According to the present invention, when applied as an interlayer insulating film of a semiconductor device, the layers are high without increasing the effective dielectric constant of the semiconductor device and without deteriorating the performance of the film adjacent to the interlayer insulating film. A laminated structure showing adhesion, a semiconductor device using the same, and a method for manufacturing the same can be provided.

  Next, embodiments of the present invention will be described in detail with reference to the drawings. The following structural drawings all schematically show embodiments of the present invention, and the dimensions of the structure according to the present invention are not defined by the ratios of the constituent elements on the drawing.

[First Embodiment]
[Construction]
Referring to FIG. 1, a cross-sectional view of a semiconductor device is shown as a first embodiment of the present invention.
A second insulating film 2 containing Si, C and O is formed on the first insulating film 1 containing Si and C, and contact between the first insulating film and the second insulating film Above and below the interface, transition layers having different composition ratios of the first insulating film 1 and the second insulating film 2 are provided.

  As shown in FIG. 1, the transition layer includes the first transition layer 3 and the second transition layer on the first insulating film 1 across the contact interface between the first insulating film 1 and the second insulating film 2. A second transition layer 4 is formed on the insulating film 2.

The structure of the transition layer will be described below using the measurement results of X-ray photoelectron spectroscopy from the viewpoint of chemical bonding.
FIG. 2 shows the Si2p spectrum measured by X-ray photoelectron spectroscopy of the film stack structure composed of the first insulating film 1, the first transition layer 3, the second transition layer 4, and the second insulating film 2. Depth profile is shown. The definitions of the first transition layer 3 and the second transition layer 4 will be described later. In FIG. 2, the depth of 200 nm (200 × 10 ⁻⁹ m) corresponds to the contact interface between the first insulating film 1 and the second insulating film 2. Referring to FIG. 2, it can be confirmed that the binding energy is chemically shifted to a higher energy side at a depth near the contact interface between the first insulating film 1 and the second insulating film 2.

  FIG. 3 is a diagram in which the mode value of the binding energy of the Si2p spectrum of the laminated structure composed of the first insulating film 1 and the second insulating film 2 is measured by photoelectron spectroscopy and plotted in the depth direction. The first insulating film 1 has a thickness of 50 nm, and the second insulating film 2 has a thickness of 200 nm.

In FIG. 3, the depth from 0 nm to 200 nm corresponds to the second insulating film 2, and the depth from 200 nm to 250 nm corresponds to the first insulating film 1. In the region with a depth of 175 nm to 200 nm, the binding energy of Si2p is shifted to the higher energy side as compared with the second insulating film 2 (100.6 eV). Further, in the region from 200 nm to 230 nm, the mode value of the binding energy of Si2p is shifted to the high energy side as compared with the first insulating film 1 (101.9 eV). These two regions are defined as a second transition layer 4 and a first transition layer 3, respectively. The chemical shift of the Si2p spectral peak toward the high bond energy is due to a chemical bond state close to SiO ₂ (103.4 eV).

  In the depth direction profile of the peak intensity of the O1s spectrum shown in FIG. 4, the peak intensity of O1s is strong in the regions of the first transition tank 3 and the second transition layer 4. This means that more oxygen atoms are present in the first and second transition layers 3 and 4 than in the first and second insulating films 1 and 2.

The presence of this oxygen atom strengthens the adhesion between the first insulating film 1 and the second insulating film 2. That is, since the first and second transition layers 3 and 4 having similar compositions are formed across the contact interface between the adjacent first insulating film 1 and the second insulating film 2, The adhesion between the first and second insulating films 1 and 2 is improved.
In addition, since the bond energy between silicon and oxygen is higher than the bond energy between silicon and nitrogen or the bond energy between silicon and carbon, the first insulating film and the second insulating film depend on the strength of the chemical bonding force. This brings about the effect that the adhesiveness with is strengthened. Furthermore, the semiconductor device having the above structure can suppress an increase in effective dielectric constant and does not lower the insulation resistance of the film or increase the hygroscopicity compared to a semiconductor device formed by a conventional method. Low leakage characteristics can be obtained. Therefore, strong adhesion can be obtained without degrading the electrical performance of the semiconductor device, and the reliability of the semiconductor device can be improved.

  Note that the thickness of the transition layer according to the present embodiment is preferably 70% or less of the thickness of the insulating film including the transition layer before the transition layer is formed. When a copper wiring cap film (such as a SiCN film) having a lower oxygen atom content than the silicon dioxide film is used as the first insulating film, the thickness of the first transition layer containing oxygen atoms exceeds 70%. In addition, after the copper wiring is formed, the presence of oxygen atoms in the film reduces the diffusion resistance of the cap film to copper, which deteriorates the electrical reliability of the semiconductor device. This also applies to the insulating films of the other embodiments.

[Production method]
Next, the manufacturing method of the first embodiment will be described with reference to FIG.
First, as shown in FIG. 5A, the first insulating film 1 is formed. The first insulating film 1 is a film containing Si and C. When forming a multilayer wiring structure, in many cases, the first insulating film 1 becomes a cap film of a lower layer metal wiring material (for example, copper or an alloy containing copper as a main component). SiC, SiCN, benzocyclobutene, etc. are suitable. Depending on the structure of the multilayer wiring, an insulating film containing Si, C, and O may be used as the first insulating film 1. Moreover, as a formation method of the 1st insulating film 1, a chemical vapor deposition method, a plasma polymerization method, etc. are mentioned.

  Next, as shown in FIG. 5B, a coating film 5 for forming a second insulating film is formed on the first insulating film 1 formed as described above so as to be an interlayer insulating film later. To do. As a coating solution for forming the second insulating film 2, a coating solution for forming an insulating film containing Si, C, and an organic solvent can be used. Further, this coating solution may be a material that can form pores of 30 nm or less in the second insulating film 2 in order to reduce the relative dielectric constant of the second insulating film 2 to be formed later. . The method of forming holes in the second insulating film 2 is roughly divided into two. One is a temperature at which the pyrolyzed polymer is dispersed in advance in the film-forming composition (that is, the coating solution for the coating film 5), and the pyrolyzed polymer is thermally decomposed after the coating film 5 is formed. This is a method of forming pores by firing with. The other is to apply a film-forming composition having a molecular structure capable of forming vacancies. In the present invention, any of the above types can be used for the film-forming composition.

  Due to the presence of the fine holes, the relative dielectric constant of the second insulating film 2 can be reduced. As a method of forming the coating film 5 for forming the second insulating film 2, a spin coating method, a scan coating method, a spray method, a dipping method, or the like is used. The film thickness of the coating film 5 at this time is about 0.01 μm to 2.0 μm. Further, the coating film 5 having a film thickness of about 2 to 10 μm may be formed by repeating the coating a plurality of times according to the film thickness required by the semiconductor device to be applied.

  Thereafter, in order to remove at least a part of the solvent in the coating solution, it is preferable to dry the substrate at room temperature or to heat the substrate using a hot plate at a temperature and time enough to evaporate the solvent. The heating temperature and time may be set to a temperature and time enough to remove the solvent contained in the film-forming coating solution, but it is preferable to carry out the heating in a short time from the viewpoint of throughput. The heating step is not intended to completely remove the solvent of the film-forming coating solution, and the solvent may remain.

  Next, as shown in FIG.5 (c), the ultraviolet-ray 6 is irradiated from the top of the coating film 5 with respect to the board | substrate produced in this way. As the output and irradiation time, it is preferable that the output and the irradiation time be shorter than those when the organic groups in the coating film 5 are eliminated. Desorption of chemical species including carbon from the coating film 5 due to ultraviolet irradiation is not preferable because the relative dielectric constant of the second insulating film 2 to be formed later increases. Moreover, if the output is too low or the irradiation time is too short, the chemical reaction for creating the first and second transition tanks 3 and 4 is not promoted, which is not preferable. The wavelength of the ultraviolet ray 6 is preferably 200 nm to 600 nm, which is a wavelength region of a commonly used ultraviolet ray source.

  As the light source of the ultraviolet ray 6, a low-pressure mercury lamp, a high-pressure mercury lamp, a metal halide lamp, a xenon lamp, a deuterium lamp, an excimer lamp, or the like can be used. Further, the substrate temperature at the time of ultraviolet irradiation is more preferably controlled to a temperature of room temperature or higher by the hot plate 7 in order to further promote the chemical reaction for forming the first and second transition layers 3 and 4. The substrate temperature is set to a temperature lower than the temperature at which the chemical species containing carbon in the coating film 5 undergoes thermal desorption and the film becomes dense. In addition, since the reaction which forms the 1st and 2nd transition layers 3 and 4 is accelerated | stimulated by heating so that a substrate temperature may become higher than room temperature, a throughput improves.

  The atmosphere for ultraviolet irradiation is preferably in a gas containing oxygen, and may be performed in the air. Further, it can also be performed in a nitrogen atmosphere in which the oxygen concentration is controlled or in an argon atmosphere in which the oxygen concentration is controlled. The ultraviolet irradiation may be performed for a time sufficient to obtain the effect of the present invention. If the ultraviolet irradiation is performed longer than the necessary time, the throughput deteriorates and, in addition, when the substrate temperature is high, the second is performed. Since the relative dielectric constant increases when the insulating film 2 becomes dense, it is not preferable.

  As shown in FIG. 5D, the first transition layer 3 and the second transition layer 4 are formed by the ultraviolet irradiation. The ultraviolet irradiation step may be performed after the final baking of the coating film 5 that follows, but a higher effect can be obtained by performing it before the final baking. This is because when the crosslinking reaction is incomplete or when the solvent remains in the coating film 5, more oxygen atoms are implanted into the interface between the coating film 5 and the first insulating film 1, and This is because the first transition layer 3 and the second transition layer 4 are easily formed.

  Finally, in order to promote the cross-linking reaction for making the film-forming composition in the coating film 5 into the second insulating film 2, and the film-forming composition in the coating film 5 has micropores inside. In order to remove the organic polymer which is a spacer for the purpose of formation, as shown in FIG. 5 (e), the temperature is optimum for promoting the crosslinking reaction, or for forming fine pores. Firing is performed at a temperature at which the spacer is thermally decomposed. The film-forming composition in the coating film 5 is converted into the second insulating film 2 while the first transition layer 3 and the second transition layer 4 are formed by the firing step.

  As a firing method at this time, a hot plate, an oven, a furnace, or the like can be used, and a firing atmosphere can be performed in nitrogen, vacuum, argon, or the like. The firing temperature and firing time depend on the material composition of the film-forming composition in the coating film 5, and are a temperature and time sufficient to improve the crosslinking density, or a temperature at which spacers for pore formation can be removed. And time. The firing time is preferably shorter from the viewpoint of throughput.

  The effect of the present invention can also be obtained when an insulating film created by a CVD method or a plasma polymerization method is used as the second insulating film 2. When an insulating film formed by the above-described CVD method or plasma polymerization method is used as the second insulating film 2, ultraviolet irradiation is performed after the second insulating film 2 is deposited. In addition, when the second insulating film 2 is formed by a film forming method that does not require final baking (such as a CVD method or a plasma polymerization method), baking is not particularly required unlike the case of the spin coating method.

[effect]
When the film laminated structure formed by the above method is observed by X-ray photoelectron spectroscopy and a transmission electron microscope (TEM), the contact interface between the first insulating film 1 and the second insulating film 2 is sandwiched. It was confirmed that the first and second transition layers 3 and 4 were formed above and below about 1 nm to 30 nm.

  Next, a method for evaluating the adhesion strength at the interface between the first insulating film 1 and the second insulating film 2 will be described. FIG. 6 is a perspective view of the measurement system. In this description, the adhesion strength between the first insulating film and the second insulating film is measured in the film laminated structure of the first insulating film 1 and the second insulating film 2 formed on the silicon substrate 8. An example is shown. First, as shown in FIG. 6A, a silicon substrate 9 is bonded to the second insulating film 2 with an epoxy resin, and a notch 10 is made in advance in the silicon wafer on the fulcrums 13 and 14 side. Next, as shown in FIG. 6 (b), the fulcrum 13 and 14 on the notched side are lowered at a constant rate while monitoring the force applied to the system with the fulcrum at 11, 12, 13 and 14. As you go, the force on the system increases. Thereafter, the upper silicon substrate 9 is broken, but at this time, the force applied to the system is relaxed and lowered. Thereafter, peeling of the film occurs at the interface between the first insulating film 1 and the second insulating film 2, but mechanical energy applied to the system is consumed for peeling of the film while the peeling occurs. Therefore, the force received by the system is a constant value. By measuring the force applied to the system at this time and substituting the parameters of the measurement system, the physical properties of silicon, and the load into Equation (1), the adhesion strength between the films can be obtained as the interfacial fracture energy Gc.

  In Equation (1), E represents the elastic modulus of the silicon substrates 8 and 9, and ν represents the Poisson's ratio of the silicon substrates 8 and 9. This method is described in detail, for example, in the June 2002 International Interconnect Technology Conference p. 242 (Proceedings of 2002 International Interconnect Technology Conference p.242).

  The adhesion strength at the interface between the first insulating film 1 and the second insulating film 2 is a normal manufacturing method (in other words, in the case where no treatment for improving adhesion is performed, in other words, a manufacturing method in which insulating films are simply laminated together). It can be confirmed by the above-mentioned four-point bending method that the layered structure formed by (Method) is improved.

Next, from the viewpoint of the rate of increase in effective relative dielectric constant, the conventional method and this embodiment compare the film stack structure, manufacturing method, and effects of the semiconductor device, and clarify the superiority of the film stack structure according to this embodiment. To do.
The film stack structure of the semiconductor device according to the present embodiment is shown in FIG. A SiCN film having a relative dielectric constant of 4.9 and a film thickness of 50 nm is prepared as the first insulating film 1 and is made of Si, O, C, and H by the method shown in this embodiment, and has a relative dielectric constant of 2.8. The second insulating film 2, the first transition layer 3, and the second transition layer 4 having a thickness of 100 nm were formed. From the measurement result by X-ray photoelectron spectroscopy, it was found that the first and second transition layers 3 and 4 have compositions close to SiO ₂ (relative dielectric constant 4.2). The above film laminated structure will be referred to as a first film laminated structure in the following description. For the first film stack structure, as shown in FIG. 7B, copper wirings 15 and 16 are formed, the inter-wiring capacitance in the lateral direction (inter-wiring direction) is measured, and based on the inter-wiring capacitance measurement result. The effective relative dielectric constant between the wirings was calculated to be 3.68.

  Next, FIG. 8A shows a film stack structure according to Patent Document 1. FIG. An SiCN film having a relative dielectric constant of 4.9 and a film thickness of 50 nm is prepared as the first insulating film 1 ′, and plasma irradiation is performed on the first insulating film 1 ′ by the method described in Patent Document 1. The substrate surface was modified to form a first transition layer 3 ′. From the measurement by X-ray photoelectron spectroscopy, the surface of the first transition layer 3 ′ was found to have a composition close to that of a SiN film (relative dielectric constant 7.5), with dissociation of carbon being observed. Next, a 100 nm thick second insulating film 2 ′ made of Si, O, C, and H and having a relative dielectric constant of 2.8 was deposited on the first insulating film 1 ′ whose surface was modified. The above film laminated structure will be referred to as a second film laminated structure in the following description. For the second film stack structure, as shown in FIG. 8 (b), copper wirings 15 and 16 are formed, the inter-wire capacitance in the lateral direction (inter-wiring direction) is measured, and the inter-wiring capacitance measurement result is measured. The effective relative dielectric constant between the wirings was calculated to be 3.74.

  On the other hand, FIG. 9A shows a film stack structure formed on the base substrate without any surface treatment. A SiCN film having a relative dielectric constant of 4.9 and a film thickness of 50 nm is prepared as the first insulating film 1 ″, and no surface treatment is performed on the substrate surface, and a second insulating film having a relative dielectric constant of 2.8. 2 ″ was deposited to a thickness of 100 nm to form a laminated film structure. This film laminated structure is defined as a third film laminated structure. For the third film stack structure, as shown in FIG. 9B, copper wirings 15 and 16 are formed, the inter-wire capacitance in the lateral direction (inter-wiring direction) is measured, and the inter-wire capacitance measurement result The effective relative dielectric constant between the wirings was calculated to be 3.65.

  Comparing the effective relative permittivity in the lateral direction (inter-wiring direction) of the above three types of film laminated structures, the first film laminated structure is 3.68, the second film laminated structure is 3.74, and the third film The laminated structure was 3.65. Since the modified layer having a higher relative dielectric constant than that of the second insulating film 2 ″ is not formed in the third film laminated structure in which the adhesion enhancing process is not performed, the first insulating film 1 ″ and the second insulating film 2 ″ are not formed. The adhesion to the insulating film 2 ″ is the lowest, but the effective relative dielectric constant is the lowest. When the increase rate of the effective relative dielectric constant of the first and second film laminated structures subjected to the adhesion strengthening process is calculated for the third film laminated structure, the first film laminated structure is about 0.8%. The second film stack structure is about 2.5%, and the first film stack structure, which is the film stack structure of the semiconductor device according to the present embodiment, is more than the second film stack structure according to the conventional method. It can be seen that the increase in effective relative permittivity can be suppressed.

[Example]
Next, a film stacking structure included in the semiconductor device will be described using a specific example of the semiconductor device according to the present embodiment. In addition, this invention is not restrict | limited at all by these Examples.
As a base substrate, a SiCN film deposited on a silicon wafer by a CVD method using a CVD apparatus Producer manufactured by Applied Materials was prepared. The composition of this film was Si (24 atomic%), C (22 atomic%), N (15 atomic%), and H (39 atomic%). On this base substrate, using ACT8-SOD manufactured by Tokyo Electron Co., Ltd., polymethylsilazane (-(SiCH ₃ ) ₂ (NH) ₃ ) _n − shown by the following structural formula (I) _n − ) And a solvent (di-butyl ether), and a coating film was formed by spin coating.

Next, in order to remove di-butyl ether as a solvent, the substrate was baked for 2 minutes in the air at a substrate temperature of 150 ° C. using a hot plate mounted on ACT8-SOD. The semiconductor substrate thus obtained was irradiated with ultraviolet rays for 30 seconds in a substrate temperature of 50 ° C. in an air atmosphere using Unihard manufactured by USHIO INC. Next, in order to replace the NH group in the interlayer insulating film with the OH group, a humidification process was performed for 30 minutes under the conditions of a substrate temperature of 50 ° C. and a humidity of 80% using a single-wafer humidifier manufactured by Tokyo Electron Co., Ltd. . Finally, in order to promote the dehydration condensation reaction of silanol groups, firing was performed in a nitrogen atmosphere at 350 ° C. for 30 minutes using furnace a-8SE manufactured by Tokyo Electron Ltd. The adhesion energy between the interlayer insulating film and the base substrate interface of the film thus obtained was measured by the four-point bending method shown in FIG. 6 and found to be 3.19 J / m ² .
Further, the chemical bonding state between the interlayer insulating film obtained by the above method and the base substrate interface was measured by photoelectron spectroscopy, and the mode of Si2p binding energy was plotted with respect to the depth direction. The characteristic indicated by the solid line was obtained.

[Comparative example]
A SiCN film deposited by the CVD method using a CVD apparatus Producer manufactured by Applied Materials was prepared as the base substrate. The composition of this film was Si (24 atomic%), C (22 atomic%), N (15 atomic%), and H (39 atomic%). On this base substrate, using ACT8-SOD manufactured by Tokyo Electron Co., Ltd., using a coating solution composed of polymethylsilazane represented by the above formula molecular formula (I) and a solvent (dibutyl ether), and by spin coating method A coating film was formed. Next, in order to remove the solvent, the substrate was baked for 2 minutes in the air at a substrate temperature of 150 ° C. using a hot plate. Next, in order to replace the NH group in the interlayer insulating film with the OH group, a humidification process is performed for 30 minutes under the conditions of a substrate temperature of 50 ° C. and a humidity of 80% using a single wafer humidifier manufactured by Tokyo Electron Co., Ltd. Went. Finally, in order to promote the dehydration condensation reaction of the silanol group, firing was performed in a nitrogen atmosphere at a temperature of 350 ° C. for 30 minutes using a-8SE manufactured by Tokyo Electron Co., Ltd. The adhesion energy between the interlayer insulating film and the base substrate interface of the film thus obtained was measured by the 4-point bending method shown in FIG. 6 and found to be 2.76 J / m ² .
Further, the chemical bonding state between the interlayer insulating film obtained by the above method and the base substrate interface was measured by photoelectron spectroscopy, and the mode of Si2p binding energy was plotted with respect to the depth direction. The characteristic indicated by the dotted line was obtained.

With reference to the depth profile of the XPS (X-ray Photoelectron Spectroscopy) spectrum of Si2p shown in FIG. 10, a clear difference can be confirmed between the above example and the comparative example.
In the film laminated structure of the comparative example that does not irradiate ultraviolet rays, no change in the mode value of the binding energy is observed at the contact interface between the interlayer insulating film and the base substrate. On the other hand, in the film laminated structure of the example irradiated with ultraviolet rays, the mode value of the binding energy is shifted to the high energy side at a depth of 200 nm corresponding to the contact interface between the interlayer insulating film and SiCN. This indicates that a transition layer having a high oxygen content is formed on each of the interlayer insulating film and the base substrate at the contact interface between the interlayer insulating film and the base substrate so as to face each other across the contact interface. Yes.
In addition, the adhesion strength at the interface between the first insulating film 1 and the second insulating film 2 measured by the four-point bending method is the same as that in a normal manufacturing method (in other words, when no treatment for improving adhesion is performed). Then, it was improved by about 15% compared with a method of simply laminating the first insulating film 1 and the second insulating film 2), and showed a value that can sufficiently withstand the formation of multilayer wiring.

  As described above, the first film stacked structure which is the film stacked structure of the semiconductor device according to the present embodiment has a higher relative dielectric constant than the second film stacked structure which is the film stacked structure according to the conventional method. The adhesion strength to the base substrate can be improved.

  In the above description, the case where the first and second insulating films are formed of a material containing silicon and oxygen is taken as an example. However, each of the first and second insulating films is a material containing at least silicon. Then, the same effect as described above can be obtained. The same applies to other embodiments.

[Second Embodiment]
A second embodiment in which the present invention is suitably implemented will be described. Referring to FIG. 11, a sectional view of a semiconductor device is shown as a second embodiment of the present invention.
A second insulating film 2 is formed on the first insulating film 1, and a third insulating film 17 is formed on the second insulating film. A first transition layer 3 is formed on the first insulating film 1 and a second transition layer 4 is formed on the second insulating film 2 with the contact interface between the first insulating film and the second insulating film interposed therebetween. ing. Also, at the interface between the second insulating film 2 and the third insulating film 17, the third transition layer 18 is formed on the second insulating film 2 and the third insulating film 17 is formed on the third insulating film 17 across the contact interface. Four transition layers 19 are respectively formed.

  Here, the second insulating film 2, the third insulating film 17, the third transition layer 18, and the fourth transition layer 19 are respectively the second insulation described in the first embodiment of the present invention. This corresponds to the film 2, the first insulating film 1, the second transition layer 4, and the first transition layer 3, respectively. That is, the film stack structure in the semiconductor device according to the present embodiment includes the second insulating film 2 and the insulating films adjacent to the second insulating film 2 (the first insulating film 1 and the third insulating film 17). It is understood that transition layers (3, 4 and 18, 19) are formed respectively. The transition layer serves as a structural transition layer having a similar composition to each other, thereby improving the adhesion between adjacent films. In addition, the transition layer is characterized by having a higher oxygen composition ratio than the first, second, and third insulating films 1, 2, and 17.

However, this is not the case when an SiO ₂ film is used as the third insulating film 17. At the contact interface between the second insulating film 2 and the third insulating film 17, Only the third transition layer 18 having a higher oxygen content than the second insulating film 2 is formed. The oxygen atoms can strengthen the adhesion between the second insulating film 2 and the insulating films adjacent thereto (first and third insulating films 1 and 17).

  That is, since the bond energy between silicon and oxygen is higher than the bond energy between silicon and nitrogen or the bond energy between silicon and carbon, the presence of transition layers 3, 4, 18 and 19 having a high oxygen composition ratio. This brings about an effect that the adhesiveness between the first insulating film and the second insulating film and the adhesiveness between the second insulating film and the third insulating film are strengthened. Therefore, resistance to a mechanical load applied to the semiconductor device is improved, and high reliability of the semiconductor device is realized.

[Production method]
Next, a method for manufacturing the semiconductor device according to the second embodiment will be described with reference to FIG.
The first insulating film 1 used in the second embodiment is a film containing Si and C, as in the first embodiment. When forming a multilayer wiring structure, in many cases, the first insulating film 1 becomes a cap film of a lower layer metal wiring material (for example, copper or an alloy containing copper as a main component). Need to be resistant to. For example, SiC, SiCN, and benzocyclobutene are suitable. Depending on the structure of the multilayer wiring, an insulating film containing Si, C, and O may be used as the first insulating film 1. Examples of the method for forming the first insulating film include a chemical vapor deposition method (CVD method) and a plasma polymerization method.

  Next, a second insulating film 2 is deposited on the first insulating film 1 so as to be an interlayer insulating film. As a method for forming the insulating film, the insulating film may be deposited by the coating method, the CVD method, or the plasma polymerization method described in the first embodiment.

  Next, a third insulating film 17 is deposited on the second insulating film 2 as a hard mask layer on the substrate prepared as described above. The purpose of the hard mask layer is to improve the coating property of an antireflection film or photoresist formed for forming a fine pattern, or to suppress damage to the second insulating film 2 during the ashing process of the photoresist. In order to reduce the damage to the second insulating film 2 in the chemical mechanical polishing step after the formation of the wiring trench and the metal film filling, it is formed. The hard mask layer needs to have mechanical strength that can withstand the chemical mechanical polishing process after embedding the metal wiring material. It is preferable to use a film containing Si and further containing at least one element selected from O, C, N and H. Further, any film having mechanical strength that can withstand the chemical mechanical polishing process and adhesion strength with the second insulating film 2 may be formed by a coating method.

  Next, the substrate prepared as described above is irradiated with ultraviolet rays 6 from above the third insulating film 17. The conditions such as the substrate temperature, atmosphere, irradiation time, and ultraviolet source at this time may be performed under the same conditions as in the first embodiment of the present invention.

  The film stacked structure of the semiconductor device according to the present embodiment formed by the above procedure (film stacked structure including the third insulating film 17, the second insulating film 2, and the first insulating film 1) is irradiated with ultraviolet rays. As a result, transition layers are formed at the respective contact interfaces between the third insulating film 17 and the second insulating film 2 and between the second insulating film 2 and the first insulating film 1. These transition layers include a first transition layer 3 formed on the first insulating film 1 and a second insulating film 2 at the contact interface between the first insulating film 1 and the second insulating film 2. The third transition layer 18 formed in the second insulating film is formed at the contact interface between the second insulating film 2 and the third insulating film 17. And a fourth transition layer 19 formed in the third insulating film.

These transition layers are characterized in that the composition ratio is different from that of the first insulating film 1, the second insulating film 2, and the third insulating film 17, and the oxygen content is large. To do. Due to the presence of the transition layer, high adhesion can be realized between the first insulating film 1 and the second insulating film 2 and between the second insulating film and the third insulating film. .
In addition, when forming the film | membrane laminated structure similar to the semiconductor device concerning this Embodiment, you may perform an ultraviolet irradiation in several times. For example, after the second insulating film 2 is formed (FIG. 9B) and after the third insulating film 17 is formed (FIG. 9D), ultraviolet irradiation is performed between the films. Adhesion can be further improved.

[Third Embodiment]
A third embodiment in which the present invention is preferably implemented will be described. Referring to FIG. 13, a cross-sectional view of a semiconductor device is shown as a third embodiment of the present invention.
A second insulating film 2 is formed on the first insulating film 1, and a third insulating film 17 is formed on the second insulating film 2. Further, the first insulating film 1, the second insulating film 2, and the third insulating film 17 are formed with wiring grooves 20 for forming metal wiring, and the side surfaces of the wiring grooves (openings) 20. The fourth insulating film 21 is formed so as to cover the side surface of the opened wiring trench 20. In the wiring groove 20, a barrier metal for preventing diffusion of metal atoms and ions to the first insulating film 1 and the second insulating film 2 is formed in a later step, and further, the main conductivity of the metal wiring is formed. As a layer, copper or an alloy containing copper as a main component is embedded.

  According to the third embodiment of the present invention, the transition layer is formed at the interface between the second insulating film 2 and the adjacent films (first, third, and fourth insulating films 1, 17, and 21). Is formed. That is, at the contact interface between the first insulating film 1 and the second insulating film 2, the first transition layer 3 is formed on the first insulating film 1, and the second transition layer 4 is formed on the second insulating film 2. Are formed, and at the contact interface between the second insulating film 2 and the third insulating film 17, the third transition layer 18 is formed on the second insulating film 2 and the third insulating film is formed on the third insulating film. 4 transition layers 19 are respectively formed, and at the contact interface between the second insulating film 2 and the fourth insulating film 21, a fifth transition layer 22 is formed on the second insulating film 2. A sixth transition layer 23 is formed on each insulating film.

  Here, the second insulating film 2, the third insulating film 17, and the fourth insulating film 21 are respectively the second insulating film 2, the first insulating film 1 and the first insulating film 1 according to the first aspect of the present invention. The third transition layer 18, the fourth transition layer 19, the fifth transition layer 22, and the sixth transition layer 23 respectively correspond to the first insulating film 1, respectively. This corresponds to the second transition layer 4, the first transition layer 3, the second transition layer 4, and the first transition layer 3, respectively.

That is, the layer stack structure in the present embodiment has a transition layer at the interface between the second insulating film 2 and the insulating films adjacent thereto (first, third and fourth insulating films 1, 17 and 21). It is understood that is formed. The transition layer serves as a structural transition layer having a similar composition to each other, thereby improving the adhesion between adjacent films. In the transition layer, the oxygen content is higher than that of the second insulating film 2 and the adjacent film. However, this is not the case when an SiO ₂ film is used as the third insulating film 17. At the contact interface between the second insulating film 2 and the third insulating film 17, Only the third transition layer 18 having a higher oxygen composition ratio than the second insulating film 2 is formed.

  Due to the presence of the oxygen atoms, the adhesion between the second insulating film 2 and the adjacent films (first, third and fourth insulating films 1, 17, and 21) can be strengthened. . That is, since the bond energy between silicon and oxygen is higher than the bond energy between silicon and nitrogen or the bond energy between silicon and carbon, the presence of oxygen atoms in the transition layer causes the second insulating film to be the second interlayer insulating film. This brings about an effect that the adhesion between the insulating film 2 and the first, third, and fourth insulating films adjacent to the second insulating film 2 is strengthened.

  In the semiconductor device according to the present embodiment, due to the presence of the transition layer in the film stack structure, the adhesion between the interlayer insulating film and the film adjacent to the interlayer insulating film becomes strong. Therefore, resistance to a mechanical load applied to the semiconductor device is improved, and high reliability of the semiconductor device is realized.

[Production method]
Next, a method for manufacturing a semiconductor device according to the third embodiment will be described with reference to FIG. The first insulating film 1 used in the third embodiment is a film containing Si and C, as in the first and second embodiments. When forming a multilayer wiring structure, in many cases, the first insulating film 1 becomes a cap film of a lower layer metal wiring material (for example, copper or an alloy containing copper as a main component). Need to be resistant to. For example, SiC, SiCN, and benzocyclobutene are suitable. Depending on the structure of the multilayer wiring, an insulating film containing Si, C, and O may be used as the first insulating film 1. Examples of the method for forming the first insulating film 1 include chemical vapor deposition (CVD) and plasma polymerization. In the case of the semiconductor device having the wiring structure shown in FIG. 13, the first insulating film 1 corresponds to the cap film of the lower wiring, and is a contact interlayer film indicated by reference numeral 24 in FIG. 13 and FIG. It is formed on the lower layer wiring or via hard mask, or the lower layer wiring or via interlayer insulating film.

  Next, a second insulating film 2 is deposited on the first insulating film 1 so as to be an interlayer insulating film. As a method for forming the second insulating film 2, the second insulating film 2 may be deposited by the coating method, the CVD method, or the plasma polymerization method described in the first embodiment.

  Next, a third insulating film 17 is deposited on the second insulating film 2 to serve as a hard mask on the substrate thus prepared. The film composition and physical properties for forming the hard mask layer are the same as those described in the second embodiment of the present invention.

  Next, as shown in FIG. 14B, wiring grooves 20 are formed along the desired fine pattern on the substrate prepared as described above. As a method for forming the wiring groove 20 along the fine pattern, a mask pattern formation by photolithography generally used and a plasma etching method subsequent thereto are usually used. FIG. 14B is a schematic diagram of plasma etching using the photoresist 26 and the third insulating film 17 patterned using the photoresist as a mask.

  According to the third embodiment of the present invention, in order to deposit the fourth insulating film 21 which will be an insulating film barrier later, resist ashing is performed simultaneously with or after the etching to remove the photoresist 26. Is preferred. In the semiconductor device according to the present embodiment, the method for forming such a fine pattern is not limited to the above, but other fine pattern forming methods such as a wet etching method, a photosensitive interlayer insulating film, and the like. It is also possible to use a direct patterning method or the like using as the second insulating film 2.

  After the wiring opening is formed, as shown in FIG. 14C, a fourth insulating film 21 is deposited in the opening 20 for forming the metal wiring to serve as an insulating film barrier. The fourth insulating film 21 is formed for the purpose of improving the time-dependent dielectric breakdown life (TDDB), particularly when the second insulating film 2 has fine holes therein. As a material for the fourth insulating film 21, a film containing Si and C or N is used, but it is more preferable that the fourth insulating film 21 has copper diffusion resistance. Examples of these include SiCN films and SiC films by CVD, and benzocyclobutene by plasma polymerization. The example described above is an example of an insulating film barrier, and the insulating film barrier material used in the semiconductor device according to the present embodiment is not limited to the above. As a method for forming the insulating film barrier (fourth insulating film 21), a sputtering method, a CVD method, an atomic layer deposition method (hereinafter referred to as ALD method), a plasma polymerization method, or the like is preferable. The method for forming the barrier material used in the above is not limited to the above.

  After the wiring trench 20 (opening) and the insulating film barrier (fourth insulating film 21) are formed as described above, the substrate 6 is irradiated with ultraviolet rays 6 as shown in FIG. The conditions such as the substrate temperature, atmosphere, irradiation time, and ultraviolet source at this time may be performed under the same conditions as in the first embodiment of the present invention.

  Next, in order to connect the lower layer wiring or via or contact and the wiring trench, the first insulating film 1 is etched by plasma etching to finally form the structure shown in FIG. The etching process may be performed before the ultraviolet irradiation process.

  The wiring structure of the semiconductor device according to the present embodiment formed by the above procedure (in addition to the configuration similar to the second embodiment, the wiring groove 20 (opening) and the insulating film barrier (fourth insulating film 21) are further provided. The film laminated structure has the second insulating film 2 and the films adjacent to the second insulating film 2 (first, third and fourth insulating films 1, 17, 21) by performing ultraviolet irradiation. ) To the first to sixth transition layers 3, 4, 17, 18, 22 and 23. These transition layers are formed on the first transition layer 3 formed on the first insulating film 1 and on the second insulating film 2 at the interface between the first insulating film 1 and the second insulating film 2. A third transition layer 18 formed on the second insulating film 2 at the interface between the second insulating film 2 and the third insulating film 17; The fourth transition layer 19 is formed on the third insulating film 17, and is formed on the second insulating film 2 at the interface between the second insulating film 2 and the fourth insulating film 21. The fifth transition layer 22 and the sixth transition layer 23 formed on the fourth insulating film 17 are configured, and at the interface between the third insulating film 17 and the fourth insulating film 21, the fourth transition layer 22 is formed. Transition layer 19 and sixth transition layer 23.

These transition layers serve as a structural transition layer having a similar composition to each other, thereby improving the adhesion between adjacent films. In addition, these transition layers are characterized by having a higher oxygen content than the first, second, third, and fourth insulating films 1, 2, 17, and 21 before the transition layer is formed. To do. Due to the presence of the transition layer, between the first insulating film 1 and the second insulating film 2, between the second insulating film and the third insulating film, and between the second insulating film and the fourth insulating film. And high adhesion between the third insulating film and the fourth insulating film.
Note that the ultraviolet irradiation in this embodiment may be performed in a plurality of times. For example, after forming the second insulating film 2, after forming the third insulating film 17, and after forming the fourth insulating film 21, ultraviolet irradiation is performed to further increase the adhesion between the films. It is done.

Each of the above embodiments is an example of a preferred embodiment of the present invention, and the present invention is not limited to these.
For example, the number of insulating films stacked is not limited to the two or three layers shown in the above embodiments, and even when four or more insulating films are stacked, ultraviolet rays are irradiated in the same manner as described above. A transition layer can be formed.
In a configuration in which four or more insulating films are stacked (a configuration having three or more interfaces between insulating films), transition layers may be formed at each interface after all insulating films have been stacked. For at least some of the interfaces, a transition layer may be formed before the uppermost insulating film is formed.
As described above, the present invention can be variously modified.

  Note that, as an application example of the present invention, a semiconductor device having a transistor and a multilayer wiring can be used for multilayer wiring. A transition layer is formed at the interface between the interlayer insulating film constituting the multilayer wiring and the film adjacent to the interlayer insulating film to improve adhesion. Further, the manufacturing method and structure according to the present invention do not increase the effective dielectric constant and do not decrease the insulation resistance and moisture absorption of the film, so that the low dielectric constant and low leakage characteristics are maintained, Improves resistance to a mechanical load applied to the semiconductor device and realizes high reliability of the semiconductor device.

Sectional drawing which shows 1st Embodiment of the semiconductor device of this invention. The measurement result of the Si2p spectrum by the X-ray photoelectron spectroscopy in 1st Embodiment of the semiconductor device of this invention. The measurement result of the Si2p spectrum by the X-ray photoelectron spectroscopy in 1st Embodiment of the semiconductor device of this invention. The measurement result by the X-ray photoelectron spectroscopy of O1s spectrum peak intensity in 1st Embodiment of the semiconductor device of this invention. FIG. 3 is a process diagram showing a method for manufacturing the semiconductor device according to the first embodiment of the present invention. Explanatory drawing of adhesive evaluation by a 4-point bending method. FIG. 3 is a cross-sectional view of a structure according to the present invention and a diagram showing an effective relative dielectric constant. Sectional drawing of the structure by the conventional manufacturing method, and the figure which showed the effective dielectric constant. Sectional drawing of the structure created with the manufacturing method which does not perform an adhesive reinforcement process, and the figure which showed the effective dielectric constant. The spectrum result by the X ray photoelectron spectroscopy which shows the comparison with the Example and comparative example of this invention. Sectional drawing which shows the 2nd Embodiment of this invention. Process drawing which shows the manufacturing method of the semiconductor device of the 2nd Embodiment of this invention. Sectional drawing which shows the 3rd Embodiment of this invention. Process drawing which shows the manufacturing method of the semiconductor device of the 3rd Embodiment of this invention. The structure figure of a prior art example (patent document 2).

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 1st insulating film 2 2nd insulating film 3 1st transition layer 4 2nd transition layer 5 Coating film for insulating film formation 6 Ultraviolet light 7 Hot plate 8 Silicon substrate 9 Silicon substrate 10 Notch 11 Support point 12 Support point 13 Support point 13 Support point 14 fulcrum 15 copper wiring 16 copper wiring 17 third insulating film 18 third transition layer 19 fourth transition layer 20 wiring groove 21 fourth insulating film 22 fifth transition layer 23 sixth transition layer 24 lower layer wiring Alternatively, a hard mask of the lower via or an interlayer insulating film 25 etching plasma 26 photoresist 27 etching plasma 28 inorganic dielectric film 29 organic dielectric film 30 inorganic dielectric film (adhesion layer)
31 Substrate to be treated

Claims (19)

First and second insulating films each containing at least silicon and formed to overlap each other;
A first transition layer formed at an interface with the second insulating film;
A second transition layer formed at the interface with the first insulating film,
The content of at least one kind of element contained in common in the first and second transition layers is such that the first insulating layer in the first transition layer and the second in the second transition layer. and the insulating film, unlike respectively,
The first and second transition layers each contain oxygen atoms, the first transition layer has a higher oxygen atom content than the first insulating film, and the second transition layer has the first transition layer. 2. A laminated structure having a higher oxygen atom content than the insulating film of 2 . The thickness of the first transition layer is 70% or less of the thickness of the first insulating film before forming the first transition layer,
2. The stacked structure according to claim 1, wherein the thickness of the second transition layer is 70% or less of the thickness of the second insulating film before forming the second transition layer. A first insulating film containing at least silicon;
A second insulating film containing at least silicon and formed by firing a coating film applied on the first insulating film;
A first transition layer formed at an interface with the second insulating film by altering a part of the first insulating film;
A second transition layer formed at the interface with the first insulating film by altering a part of the coating film before firing,
The content of at least one kind of element contained in common in the first and second transition layers is such that the first insulating layer in the first transition layer and the second in the second transition layer. A laminated structure characterized by being different from the insulating film. The thickness of the first transition layer is 70% or less of the thickness of the first insulating film before forming the first transition layer,
The thickness of the said 2nd transition layer is 70% or less of the film thickness of the said coating film before this 2nd transition layer formation, The laminated structure of Claim 3 characterized by the above-mentioned. A third insulating film containing at least silicon and formed on the second insulating film;
A third transition layer formed at the interface with the third insulating film by altering a part of the second insulating film;
A fourth transition layer formed at the interface with the second insulating film by altering a part of the third insulating film,
The content of at least one element contained in common in the second and third transition layers is such that the third transition layer has the second insulating film and the fourth transition layer has the third content. The laminated structure according to any one of claims 1 to 4 , wherein the laminated structure is different from each of the insulating films. First and second insulating films each containing at least silicon and formed to overlap each other;
A first transition layer formed at an interface with the second insulating film;
A second transition layer formed at the interface with the first insulating film,
The content of at least one kind of element contained in common in the first and second transition layers is such that the first insulating layer in the first transition layer and the second in the second transition layer. Different from the insulation film of
A third insulating film containing at least silicon and formed on the second insulating film;
A third transition layer formed at the interface with the third insulating film by altering a part of the second insulating film;
A fourth transition layer formed at the interface with the second insulating film by altering a part of the third insulating film,
The content of at least one element contained in common in the second and third transition layers is such that the third transition layer has the second insulating film and the fourth transition layer has the third content. the insulating film and the product layer structure being different from each. The third and fourth transition layers each contain oxygen atoms, the third transition layer has a higher oxygen atom content than the second insulating film, and the fourth transition layer has the first transition layer. 7. The laminated structure according to claim 5, wherein the oxygen atom content is higher than that of the insulating film 3. The thickness of the third transition layer is 70% or less of the thickness of the second insulating film before the formation of the third transition layer,
The thickness of the fourth transition layer, any one of claims 5, characterized in that 70% or less of the film thickness of the third insulating film before the transition layer formed of said 4 7 The laminated structure according to 1. A recess formed on the third insulating film and reaching the second insulating film;
A fourth insulating film containing at least silicon and formed on the inner surface of the recess;
A fifth transition layer formed at an interface between the second insulating film and the fourth insulating film;
A sixth transition layer formed at an interface between the fourth insulating film and the second insulating film;
The content of at least one kind of element contained in common in the fifth and sixth transition layers is such that the second transition film in the fifth transition layer and the fourth in the sixth transition layer. the insulating film and the multilayer structure according to any one of claims 5 to 8, wherein each different.   The fifth and sixth transition layers each contain oxygen atoms, the fifth transition layer has a higher oxygen atom content than the third insulating film, and the sixth transition layer has the first transition layer. The laminated structure according to claim 9, wherein the oxygen atom content is higher than that of the insulating film 4. The thickness of the fifth transition layer is 70% or less of the thickness of the second insulating film before the formation of the fifth transition layer,
11. The stacked structure according to claim 9, wherein a thickness of the sixth transition layer is 70% or less of a thickness of the fourth insulating film before the sixth transition layer is formed. body.   12. The stacked structure according to claim 1, wherein a relative dielectric constant of the second insulating film is lower than a relative dielectric constant of a silicon oxide film. First and second insulating films each containing at least silicon and formed to overlap each other;
A first transition layer formed at an interface with the second insulating film;
A second transition layer formed at the interface with the first insulating film,
The content of at least one kind of element contained in common in the first and second transition layers is such that the first insulating layer in the first transition layer and the second in the second transition layer. Different from the insulation film of
A laminated structure having a relative dielectric constant of the second insulating film lower than that of a silicon oxide film . The laminated structure according to any one of claims 1 to 13 , wherein the second insulating film has a fine hole inside. Wiring of the multilayer structure to the laminated structure according to any one of claims 1 to 14 is formed, and wherein a transistor is mounted on the wiring. Forming a second insulating film containing at least silicon on the first insulating film containing at least silicon;
Irradiating the first and second insulating films with ultraviolet rays at least once in an atmosphere containing oxygen;
A method for manufacturing a semiconductor device, comprising: Forming a coating film containing at least silicon on the first insulating film containing at least silicon;
Irradiating the first insulating film and the coating film with ultraviolet light in an oxygen-containing atmosphere;
Baking the coating film;
A method for manufacturing a semiconductor device, comprising: Forming a second insulating film containing at least silicon on the first insulating film containing at least silicon;
Forming a third insulating film containing at least silicon on the second insulating film;
Irradiating the first, second and third insulating films with ultraviolet light in an oxygen-containing atmosphere;
A method for manufacturing a semiconductor device, comprising: Forming a first insulating film containing at least silicon on a silicon substrate;
Forming a second insulating film containing at least silicon on the first insulating film;
Forming a third insulating film containing at least silicon on the second insulating film;
Forming an opening extending through the third insulating film to the second insulating film, and forming a fourth insulating film containing at least silicon on the inner surface of the opening;
Irradiating the substrate and the first, second, third, and fourth insulating films with ultraviolet light in an atmosphere containing oxygen;
A method for manufacturing a semiconductor device, comprising:

Images