JP2006019316A - Pattern formation method and method for manufacturing thin film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a pattern formation method that can realize highly accurate patterning even when the film is made of photosensitive resin or the like and is thick. <P>SOLUTION: A first pattern 1 is formed on a substrate 3, and a layer 2 made of a material to be patterned is formed in the opening 4 of the first pattern 1, and then the first pattern 1 is removed to form a second pattern made of a material to be patterned. In this method, the first pattern 1 is preferably constituted such that it may be made of metal or photosensitive resin, and the material to be patterned may be organic or inorganic. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a pattern forming method made of an organic material or an inorganic material that is difficult to form a pattern, such as a non-photosensitive resin, and a method for manufacturing a thin film having a formed pattern. The present invention relates to a pattern forming method capable of patterning and a thin film manufacturing method. The present invention also relates to a pattern forming method including a step of deforming a pattern formed in a rectangular shape or the like into a desired shape, and relates to a pattern forming method for deforming a pattern applicable to a wide range of organic materials or inorganic materials.

  From the viewpoint of pattern formation, in general, the material itself has a pattern forming ability and can easily form a pattern, and the material itself has no pattern forming ability and forms a pattern. Can be classified as difficult materials. Considering resin materials (polymer materials), photosensitive resins having photosensitivity and non-photosensitive resins having no photosensitivity correspond to this classification.

  A photosensitive resin typified by a resist itself has a pattern forming ability, and thus has an advantage that a fine pattern can be easily formed. However, since the photosensitive resin is made mainly for imparting photosensitivity, it may be difficult to control mechanical properties such as tensile elongation at break and elastic properties and thermal properties over a wide range. The disadvantage is that their properties are sacrificed. On the other hand, since the non-photosensitive resin is not limited by imparting photosensitivity, those having a wide range of characteristics regarding mechanical characteristics (such as tensile elongation at break and elastic modulus) and heat resistance are available. However, since the non-photosensitive resin does not have a good pattern forming ability like the photosensitive resin, it is necessary to form the pattern by some method when the pattern needs to be formed. In addition, for materials other than resin materials, it is necessary to form a pattern by a method suitable for each material for materials that do not have pattern forming ability.

  As a conventionally known method for forming a pattern made of a non-photosensitive resin, there is an etching method. In the etching method, a photosensitive resin layer is formed on a layer formed of a non-photosensitive resin, a mask made of the photosensitive resin is formed by exposure / development, etc., and then an etching operation is performed to remove the mask opening. By removing the non-photosensitive resin, a pattern having a desired shape made of the non-photosensitive resin is formed. The etching method is also used for patterning a non-photosensitive inorganic material thin film, and can form a pattern of a desired shape made of an inorganic material.

  The etching method includes a dry etching method and a wet etching method. In the dry etching method, a non-photosensitive resin layer or an inorganic material thin film is patterned by ashing using plasma or reactive ion etching (RIE). In the wet etching method, the non-photosensitive resin layer and the inorganic material thin film are patterned by etching using various etching solutions. For example, Patent Document 1 proposes a method of etching a non-photosensitive resin with an alkali developer.

  As another pattern forming method, there is a method of patterning a non-photosensitive resin by ablation using laser light. This method is used when forming a via in a printed wiring board having a built-up layer.

  Further, as another pattern forming method, there is a method in which a mold (also referred to as a stamper) having a pattern formed on a hard surface such as a metal disk is prepared and the pattern is formed by pressing the mold against a non-photosensitive resin. For example, Patent Document 2 proposes a method of forming a resin pattern by stamping using a mold made of a hard Ni electroformed master.

On the other hand, as a method for deforming and rounding the resin pattern formed by these pattern forming methods, there is a method by heating. For example, Patent Document 3 proposes a technique for deforming a rectangular pattern into a lens shape by thermal reflow.
JP-A-11-219949 (paragraph numbers 0005, 0006, 0008, FIG. 3) JP 2004-12941 A (paragraph number 0014, FIG. 1) Japanese Patent Laying-Open No. 2003-222705 (paragraph numbers 0021 to 0023, FIG. 1)

  However, the pattern forming method of a non-photosensitive resin layer or an inorganic material thin film (hereinafter referred to as a non-photosensitive resin layer or the like) has the following problems.

  The dry etching method has a problem that it is difficult to form a highly accurate pattern when the non-photosensitive resin layer or the like becomes thick. This is because when the non-photosensitive resin layer or the like becomes thick, the etching time becomes long and side etching due to wraparound of plasma or the like becomes large, and a pattern shape that accurately reflects the mask pattern cannot be obtained. is there. In addition, since the dry etching method generally requires an operation under vacuum, there is a problem that a large and expensive apparatus is required and a vacuum process is required, which complicates the process. Furthermore, as will be described later, there is a problem that shape control in the thickness direction cannot be performed.

  The wet etching method has a problem that the types of non-photosensitive resins and inorganic materials (hereinafter referred to as non-photosensitive resins) that can be etched are remarkably limited. This is an etching that dissolves only the non-photosensitive resin without dissolving the photosensitive resin when the photosensitive resin such as a resist is used as a mask in addition to the solvent that dissolves the non-photosensitive resin or the like. This is because a combination of such a non-photosensitive resin or the like, a photosensitive resin and an etching solution is remarkably limited. Also, in the wet etching method, as in the dry etching method, the side etching tends to be large during etching, and when the side etching is particularly large, the photosensitive resin layer used as a mask hangs down or becomes free. (For example, see paragraph number 0008 of Patent Document 1).

  Further, the method using laser light has a problem that the lower layer is greatly damaged by the laser light and the heat generated by the laser light. For this reason, this method cannot be used when the lower layer is made of a material weak to laser light or heat. As an example of this, there is a case where a non-photosensitive resin layer is formed on an LSI and the non-photosensitive resin layer on the pad portion which is a wiring connection portion is removed with a laser beam. In this case, generally, the lower pad portion and further the fine wiring and semiconductor element in the lower layer are damaged by the laser beam. Further, although depending on the wavelength of the laser beam to be used, the method using the laser beam generally has a problem that only a large pattern or opening of several tens of microns or more can be formed. Furthermore, in the case of inorganic materials, there is a problem that pattern formation is difficult because of high resistance to laser light.

  Further, in the method of forming a pattern by pressing a mold against a non-photosensitive resin layer or the like, there is a problem that it is difficult to control the position of the pressing mold, and the position of the pattern is shifted due to deformation of the pressing mold. Moreover, although it is comparatively easy to form a hollow, there exists a subject that it is difficult to form the pattern containing the "hole" penetrated to the bottom part.

  On the other hand, in the method by heating as a method of rounding the edge portion of the pattern made of resin, the material that rounds the edge portion by heating is limited in thermosetting resin, etc., and the degree of roundness of the edge portion is controlled. It is even more difficult to do. In addition, when the edge portion is rounded by performing an etching operation in advance, there is a problem that the surface portion is hardened by touching the etching solution, and the edge portion is not rounded as expected only by heating.

  The present invention has been made to solve the above-described problems, and a first object of the present invention is to provide a pattern forming method capable of high-precision patterning even with a thick film made of a non-photosensitive resin or the like. Is to provide. A second object of the present invention is to provide a pattern forming method including a step of deforming a pattern formed in a rectangular shape or the like into a desired shape. A third object of the present invention is to provide a method for producing a thin film having a formed pattern.

  In the pattern forming method of the present invention for achieving the first object, a first pattern is formed on a substrate, a layer made of a material to be patterned is formed in an opening of the first pattern, and then The second pattern made of the material to be patterned is formed by removing the first pattern.

  According to the present invention, even when a non-photosensitive resin or an inorganic material that is generally difficult to pattern is used as a pattern material, a pattern (second pattern) made of the pattern material can be easily and It can be formed with high accuracy. This is particularly effective when a thick film pattern (second pattern) is formed. The “patterned material” as used in the present invention is defined as meaning the constituent material of the second pattern formed by using the first pattern as a mold.

  In the pattern forming method of the present invention, the first pattern is preferably a pattern made of metal or a pattern made of a photosensitive resin. According to the present invention, a pattern made of a metal such as copper or a pattern made of a photosensitive resin is used as the first pattern. Therefore, by removing the first pattern, a highly accurate second pattern is formed. can do.

  In the pattern forming method of the present invention, the pattern material is preferably an organic material or an inorganic material. Inorganic materials such as non-photosensitive resins or inorganic materials such as glass ceramics are generally considered difficult to pattern, but according to the present invention, even when these materials are used as pattern materials, high precision A pattern can be easily formed.

  In the pattern forming method of the present invention, the layer made of the material to be patterned is formed by applying a liquid material to be patterned, or the film-like material to be patterned is formed on the first pattern. It is preferable to form by sticking. According to the present invention, a wide range of organic materials and inorganic materials including materials that are difficult to pattern can be used as the material to be patterned.

  In the pattern forming method of the present invention, after the layer made of the pattern material forms a film that repels the pattern material on the first pattern, the pattern material is placed on the first pattern. Preferably, it is formed by applying or pasting. In the pattern forming method of the present invention, after the layer made of the pattern material is applied or pasted from the first pattern on the first pattern, the first material is mechanically or chemically treated. Preferably, the upper part of the pattern is exposed and then the first pattern is removed. According to these inventions, since the material to be patterned that prevents the first pattern formed first on the substrate from being removed does not exist on the top of the first pattern, the first pattern is It can be easily removed to efficiently form a highly accurate pattern.

  In the pattern forming method of the present invention according to the first embodiment for achieving the second object, after the second pattern made of the pattern material is formed by the above-described pattern forming method of the present invention, the pattern material The second pattern is deformed by placing it in a solvent atmosphere capable of deforming. According to the present invention, for example, a pattern (second pattern) made of a non-photosensitive resin or the like can be deformed into a form having a rounded edge portion or deformed into a corrugated shape.

  In the pattern forming method of the present invention according to the second embodiment for achieving the second object, the rectangular pattern is placed on the substrate in a solvent atmosphere capable of deforming the rectangular pattern. The pattern is deformed. According to the present invention, a rectangular pattern having a rectangular edge portion can be easily transformed into a pattern having a rounded edge portion or a waveform pattern.

  The method for producing a thin film of the present invention for achieving the third object is to form a pattern on the substrate by the pattern forming method of the present invention described above, and then remove the substrate or a layer having the pattern and the substrate And a thin film having the pattern is formed. According to the present invention, since a thin film having a pattern can be produced, it can be used for an application using the pattern.

  According to the pattern forming method of the present invention, even when a non-photosensitive resin or an inorganic material, which is generally considered difficult to be patterned, is used as a pattern material, a pattern made of the pattern material (second pattern) ) Can be formed easily and with high accuracy. In addition, the thick film pattern is particularly effective because, for example, the conventional problem that occurs because etching takes a long time can be avoided. Further, a large and expensive apparatus is not required for patterning, and the process is simplified. Further, the type of pattern material is not limited, and a difficult combination with a conventional etching solution is unnecessary, which is advantageous for patterning a wide range of pattern materials. In addition, it is possible to easily and accurately pattern a pattern material that is difficult to be patterned by etching or the like, and it is possible to easily form a pattern including a through hole (through hole).

  Further, according to the pattern forming method including the step of deforming the pattern or the like formed in the present invention into a desired shape, for example, a form having a rounded edge portion without damaging the pattern made of a non-photosensitive resin or the like It can be deformed with good control and can be deformed with good control to the waveform shape.

  Moreover, according to the method for producing a thin film of the present invention, a thin film having a pattern made of a non-photosensitive resin or an inorganic material, which is generally considered difficult to be patterned, can be produced. It can use suitably for the use using a pattern.

  Hereinafter, a pattern forming method for a non-photosensitive resin and the like and a method for producing a thin film according to the present invention will be described with reference to the drawings.

(Pattern formation method)
FIG. 1 is a process diagram showing an example of the pattern forming method of the present invention. In the pattern forming method of the present invention, first, as shown in FIG. 1A, a first pattern 1 serving as a mold is formed on a substrate 3, and then, as shown in FIG. A layer 2 made of a material to be patterned is formed in the opening 4 of the first pattern 1, and then, as shown in FIG. 1C, the first pattern 1 is removed and a second material made of the material to be patterned The pattern 2 is formed. Hereinafter, each process is demonstrated in order. In addition, in this application, the code | symbol 2 is used as what represents the layer which consists of to-be-patterned material, and a 2nd pattern.

<Formation of first pattern>
First, a process of forming the first pattern 1 on the substrate 3 (see FIG. 1A) will be described. The first pattern 1 formed in this step functions as a mold when the second pattern 2 is formed in a later step (see FIGS. 1B and 1C).

  The first pattern 1 is a pattern provided in advance on the substrate 3 in order to easily perform patterning of a non-photosensitive resin or an inorganic material, which is generally considered difficult to pattern. Therefore, the first pattern 1 is provided as an inverted shape of the pattern (second pattern 2) to be finally obtained.

  As a material for forming the first pattern 1, a metal such as copper or a photosensitive resin such as a resist is preferably used.

  The metal such as copper may be formed in a single layer or multiple layers, for example, a plating method such as electroless plating or electrolytic plating, or various types such as vapor deposition, sputtering or CVD. It can be formed on the substrate 3 by the film forming means. In particular, it is preferably formed by a plating method, and may be a plating film other than copper, such as nickel or gold. Patterning of a metal such as copper may be performed by various methods such as an additive method and a full additive method, or after forming a metal layer by various means, a resist that is a photosensitive resin is formed, and then exposure is performed. The first pattern 1 having a predetermined shape may be formed by performing development and further etching. Moreover, as shown in Example 1 described later, after forming a seed layer on a substrate, a plating resist pattern may be formed, and then a plating pattern may be formed by a plating method. For example, when a non-photosensitive resin is used as a material to be patterned, the first pattern 1 made of metal has an advantage that deformation due to a solvent that is a constituent component of the non-photosensitive resin does not occur.

  A photosensitive resin such as a resist can be formed on the substrate 3 by various methods such as spin coating, can be easily patterned by exposure and development using a mask, and can be easily removed with an alkaline solution, etc. This is advantageous in many respects. As long as it is a photosensitive resin, it may be a negative type or a positive type.

  As the substrate 3, various types such as a wafer, a glass substrate, a printed wiring board (a glass epoxy substrate, a Teflon (registered trademark) substrate, an organic substrate such as a polyimide substrate, a liquid crystal polymer substrate) and the like can be used. The type of the substrate 3 is selected depending on the use of the pattern (second pattern) to be finally obtained.

  For example, when the formed pattern has a rounded corrugated shape and the pattern is used as a stress relaxation layer on the wafer on which the semiconductor element is formed, the wafer is used as the substrate 3. Further, when the formed pattern is a pattern made of a non-photosensitive resin or the like, and the pattern is used as a microlens used for a display or the like, a transparent glass substrate or an organic substrate is used as the substrate 3. .

<Formation of layer made of pattern material>
Next, the process of forming the layer 2 made of the material to be patterned in the opening 4 of the first pattern 1 (see FIG. 1B) will be described. The layer 2 formed in this step is provided so as to be buried in the opening 4 of the first pattern 1 and is formed so as to be in contact with the side surface of the first pattern 1. In the present application, “contacting the side surface” means that the layer 2 made of the material to be patterned is substantially in contact with the side surface of the first pattern 1 patterned with high accuracy as shown in FIG. . By forming the layer 2 made of the material to be patterned in such a state, a finally obtained pattern (second pattern 2) is formed with high accuracy.

  The pattern forming method of the present invention is characterized in that the material to be patterned for forming the layer 2 is a non-photosensitive resin or an inorganic material that is generally considered difficult to pattern. Specific examples of the material to be patterned include organic materials such as non-photosensitive polyimide and non-photosensitive epoxy resin, and inorganic materials such as glass and alumina.

  As the material to be patterned, a liquid material or a film-like material is used. The liquid pattern material is convenient because it can be poured into the openings 4 of the first pattern 1. Specifically, the case where it is a resin precursor itself such as a thermosetting resin before curing or a case where a non-photosensitive resin or an inorganic material is dissolved in a solvent is included. As a coating method, spin coating or bar coating can be raised.

  Examples of the film-like material to be patterned include a dry film, and the layer 2 made of the material to be patterned is formed by pasting this dry film on the first pattern 1. Examples of the method for attaching the dry film include vacuum lamination and vacuum press.

  When the first pattern 1 is formed of a photosensitive resin and the layer 2 made of the pattern material is formed by applying an organic material such as a non-photosensitive resin, a solvent that is a constituent component of the organic material May deform the photosensitive resin. When such deformation occurs, it is preferable to confirm the compatibility between the solvent and the photosensitive resin in advance and select the type of each material so that such deformation does not occur.

  When the second pattern 2 is formed using the non-photosensitive resin as the pattern material after the first pattern 1 made of metal is formed, the non-photosensitive resin as the pattern material is There is an advantage that the metal which is the pattern 1 is not easily attacked by the etching solution when the metal is etched away.

<Formation of second pattern>
Next, the process of removing the first pattern 1 and forming the second pattern 2 made of the material to be patterned (see FIG. 1C) will be described.

  As a method of removing the first pattern 1 functioning as a mold, when the first pattern 1 is made of a material having solvent solubility, it is desirable to dissolve and remove the first pattern 1 with a solvent or the like. When the first pattern 1 is made of metal, it is desirable to remove the first pattern 1 by dissolving it with an acid-based etching agent or an alkaline etching agent.

  In order to quickly remove the first pattern 1 and form the second pattern 2 with high accuracy, it is desirable to expose the upper portion of the first pattern 1. Below, the specific aspect which can expose the upper part of the 1st pattern 1 is demonstrated.

  First aspect: When the layer 2 made of the material to be patterned is formed by coating, for example, as shown in FIG. 1B, the thickness (height) of the first pattern 1 is formed by coating. It is desirable to set it to be thicker than 2. By this means, the upper part of the first pattern 1 can be exposed.

  Second embodiment: When the layer 2 made of a pattern material is applied and formed, for example, as shown in FIG. 2, a film 6 that repels the pattern material such as a non-photosensitive resin is formed on the first pattern 1. Is preferably formed in advance. By this means, even when a liquid pattern material is applied, the pattern material is not placed on the upper portion of the first pattern 1, and the upper portion of the first pattern 1 can be exposed.

  The film 6 that repels the pattern material is preferably a film 6 made of a substance having a small critical surface tension with respect to the pattern material. Examples of such a film 6 include a fluorine-based film such as Teflon (registered trademark). Such a film 6 can be applied only to the top of the first pattern 1 using a roller or the like after the first pattern 1 is formed.

  Third Mode: When the first pattern 1 is formed by plating, for example, as shown in FIG. 3, before peeling the plating resist 7 (see FIG. 3A), a film that repels the material to be patterned A material 6 is applied onto the plating resist 7 to uniformly form the film 6 (see FIG. 3B), and then the plating resist 7 is peeled off to automatically make the first metal plating metal. A film 6 for repelling a pattern material made of, for example, a non-photosensitive resin can be formed only on the pattern 1 (see FIG. 3C). By this means, the material to be patterned is not placed on the upper part of the first pattern 1, and the upper part of the first pattern 1 can be exposed.

  Fourth Mode: As shown in FIG. 4, when the pattern material is applied on the substrate 3 on which the first pattern 1 is formed, the layer 2 of the pattern material is formed on the first pattern 1. May exist. In this case, it is preferable to remove the layer 2 on the first pattern 1 by a mechanical operation such as cutting or polishing or a chemical method. Examples of the cutting include cutting with a hard object such as a cutter blade, or cutting with a soft object. Examples of the polishing include buffing and polishing by a CMP (chemical mechanical polishing) method. Examples of the chemical method include an ashing method using radicals. By this means, the material to be patterned at the top of the first pattern 1 can be removed, so that the top of the first pattern 1 can be exposed.

  In the fourth aspect, when the layer 2 made of the pattern material exists on the first pattern 1 made of the photosensitive resin, the pattern material is mechanically operated (cutting or polishing). When it is attempted to remove, the mechanical strength of the first pattern 1 made of a photosensitive resin is not sufficient, so that there arises a problem that the pattern material cannot be cut or polished smoothly. When such a problem occurs, it is preferable to form the first pattern 1 with a metal. Since metals generally have high hardness, there is an advantage that no problem occurs even if a step of cutting or polishing a non-photosensitive resin is performed. In addition, since the metal has a high hardness, it is advantageous to use an inorganic material as the material to be patterned.

  Further, as shown in FIG. 5, in the pattern forming method of the present invention, for example, the plating pattern (first pattern 1) has a multi-step structure, and the size and width of each step are changed to change the thickness direction. It is possible to form the second pattern 2 having a changed size and width. For example, after applying a plating resist and patterning the plating resist, plating is performed, and thereafter the plating resist is removed to form a plating pattern 1a (see FIG. 5A), and then the plating resist is applied again. After coating, the plating resist is patterned so as to have a pattern having a shape or size different from the above, and then plating is performed. Thereafter, the plating resist is removed to form a plating pattern 1b (see FIG. 5B). Subsequently, a plating pattern 1c and a plating pattern 1d are sequentially formed by the same procedure (see FIG. 5C), and a first pattern 1 having a size and width changed in the thickness direction is formed (FIG. 5). 5 (C)). Next, a layer 2 made of a material to be patterned is formed in the opening 4 of the first pattern 1 by coating or the like (see FIG. 5D), and then the first pattern 1 is removed by etching or the like. Then, the second pattern 2 made of the material to be patterned is formed. The thus formed second pattern 2 made of non-photosensitive resin or the like has a structure in which the size and width are changed in the thickness direction, and has an advantage that it cannot be obtained by a normal etching method or the like.

  As described above, according to the pattern forming method of the present invention, even when a non-photosensitive resin or an inorganic material, which is generally considered difficult to pattern, is used as a pattern material, the pattern forming method is made of the pattern material. A pattern (second pattern) can be formed easily and with high accuracy. In addition, the thick film pattern is particularly effective because, for example, the conventional problem that occurs because etching takes a long time can be avoided.

(Method to change the pattern)
FIG. 6 is an explanatory diagram of a pattern forming method including a step of deforming a pattern formed in the present invention into a desired shape. If this method is grasped from one viewpoint, after the second pattern 2 is formed, the second pattern 2 is placed in a solvent atmosphere in which the pattern material constituting the second pattern 2 can be deformed. Is a method of transforming. Further, if this method is viewed from another viewpoint, the substrate 3 after forming the rectangular pattern (second pattern 2 in FIG. 6) is placed in a solvent atmosphere that can deform the rectangular pattern. This is a method of deforming a rectangular pattern.

  FIG. 6A shows a rectangular second pattern 2 formed by the method of the present invention described above. An opening 5 is formed in the second pattern 2, and the top edge 21 and the bottom edge 22 of the rectangular pattern forming the opening 5 are both rectangular. FIG. 6B shows a mode in which the second pattern 2 is deformed by placing the substrate 3 having the second pattern 2 in a solvent atmosphere.

  The solvent atmosphere is an atmosphere in which a gas component of a solvent that can deform the second pattern 2 exists. The concentration of the solvent in the atmosphere is arbitrarily adjusted within a range in which the shape of the second pattern 2 can be deformed into a desired shape, and may be close to saturation or low. Also, the ambient temperature is arbitrarily set from the degree of deformation and the gas concentration.

  For example, when the material to be patterned is a resin material, the solvent may be the same as the solvent component in the resin, but may be another solvent as long as it has deformability. As an example of the solvent when the material to be patterned is a resin material, various commonly used solvents such as acetone, methyl ethyl ketone, IPA, PGMEA, NMP, cyclohexanone, and cyclopentanone can be used. On the other hand, when the material to be patterned is an inorganic material, a solvent such as an alcohol compound can be used.

  In the present invention, it is preferable to deform the pattern (second pattern 2) so as to have a rounded shape. The degree of roundness can be controlled by the good solvent property with respect to the pattern material constituting the pattern (second pattern 2), the standing time in the solvent atmosphere, and the like. That is, the good solvent property with respect to the material to be patterned is likely to be rounded if a solvent having a high good solvent property is used, and difficult to round if a poor solvent is used. Further, if the standing time in the solvent atmosphere is lengthened, it tends to be rounded, and if the standing time is shortened, it is difficult to round. The degree of rounding can also be controlled by changing the standing temperature in a solvent atmosphere.

  By optimizing these conditions, when the top edge 21 of the initial pattern (second pattern 2) is deformed to be slightly rounded, when the entire pattern including the top edge 21 and the bottom edge 22 is deformed, Furthermore, it is possible to control until the bottom of the opening 5 of the initial pattern (second pattern 2) is completely filled and the dent 61 (see FIG. 6C) is deformed. In FIG. 6C, reference numeral 62 denotes a mode in which the top edge 21 and the bottom edge 22 are deformed, but the state of the through hole in which the bottom is not filled is maintained.

  Such deformation preferably takes various forms depending on the use of the obtained pattern. For example, when a microlens is produced by deforming a formed pattern, it is desirable to control the entire pattern to be rounded. Further, when the formed pattern is provided on the LSI in order to act as a stress relaxation structure, it is desirable that the pattern is deformed so that the upper portion thereof is wavy and a wiring is formed thereon. In addition, the width and size of the opening of the pattern can be changed depending on the location on the substrate. For example, a part of the opening can be opened like a so-called through-hole, and the other part can be formed into a hollow shape that is opened halfway, or can be a completely closed structure.

  The pattern that can be deformed may be a pattern formed by the pattern forming method according to the present invention as described above, or may be a pattern formed by a method other than the present invention. In short, any pattern that can be deformed by being placed in a solvent atmosphere may be used. Therefore, both the non-photosensitive resin and the inorganic material of the pattern material in the present invention can be applied, and further, a photosensitive resin may be used.

  You may use the pattern of a thermosetting resin as a pattern to deform | transform. In this case, since it is necessary to soften in a solvent atmosphere, it is necessary to make a state where the curing has not progressed completely. For this reason, it is desirable to intentionally shorten the curing time or limit the drying conditions to the extent that the solvent volatilizes.

  Further, the pattern before the deformation does not necessarily need to be a rectangular pattern, and any other pattern may be used as long as it undergoes deformation, and the degree of deformation may be small as necessary.

  As described above, according to the pattern forming method including the step of deforming the formed pattern into a desired shape, for example, a pattern made of non-photosensitive resin or the like can be transformed into a form having rounded edges. It can be deformed into a wave shape. As a result, for example, a pattern made of a non-photosensitive resin or the like can be deformed with good control to a form having a rounded edge without causing damage, or can be deformed with good control to a corrugated shape.

(Thin film production method)
7 and 8 are process diagrams showing an example of a method for producing a thin film of the present invention.

  FIG. 7 shows a method of forming the thin film 11 having the rounded pattern 3 by deforming the substrate 3 after the pattern 2 is formed in a solvent atmosphere and then removing the substrate 3. In FIG. 7, reference numeral 71 indicates a form in which what was originally a through-hole is filled with a bottom due to deformation, and has a so-called hollow shape.

  8 shows that the substrate 3 after the pattern 2 is formed is deformed in a solvent atmosphere, and then the layer having the rounded pattern 2 and the substrate 3 are separated, and the thin film 12 having the pattern 2 is separated. It is a method of forming. In FIG. 8, reference numeral 81 indicates a form in which a bottom that was originally a through hole is filled with a deformation, so that the bottom is formed into a so-called hollow shape. The form in which the state is maintained is shown. In this embodiment, another layer 83 is formed between the substrate 3 and the pattern 2. This layer is preferably a resin layer, but is not particularly limited.

  Specifically, a method of using a copper plate or a Si wafer as the substrate 3 and forming a pattern on the substrate 3 and then removing the substrate by etching can be mentioned. Further, a resin plate having low adhesiveness to a resin material such as polyethylene is used as the substrate 3, and after the pattern 2 made of the resin material such as polyethylene is formed on the substrate 3, the substrate 3 is peeled off. A method can be illustrated.

  By such a method, a thin film having a rounded pattern can be produced, so that it can be used for applications using the pattern.

  Hereinafter, the present invention will be described in more detail based on examples and comparative examples. Note that the present invention is not limited thereby.

Example 1
An 8-inch wafer was used as the substrate 3, and a seed layer for electroplating was formed on the substrate 3 in the order of titanium and copper by sputtering, and then a plating resist was applied. The thickness of the plating resist was 30 microns. It exposed and developed through the mask which has an opening part of a different magnitude | size, and the opening part corresponding to a predetermined pattern was formed. After forming a plating pattern as the first pattern 1 on the seed layer by electrolytic copper plating, the plating resist was peeled off, and the seed layer under the plating resist was removed by etching. The height of the plating layer was about 30 microns.

  A non-photosensitive resin (epoxy thermosetting resin, manufactured by Hitachi Chemical Co., Ltd., trade name: HIMAL), which is a pattern material, is formed on the substrate 3 on which the first pattern 1 made of a plating pattern is formed. Was applied by a spin coater so as to be 20 microns, and dried at 80 ° C. for 2 minutes. When observed with an optical microscope, the non-photosensitive resin layer (second pattern 2) was formed such that the non-photosensitive resin as the pattern material was in contact with the side surface of the plating layer as the first pattern 1. Moreover, although the thin film of non-photosensitive resin remained on the upper part of the plating layer, the thin film on the upper part of the plating layer was removed by performing plasma ashing for 10 minutes. When the wafer on which the plating pattern (first pattern 1) and the non-photosensitive resin layer (second pattern 2) are formed is dipped in a copper etching solution and a titanium etching solution, the plating pattern is opened, and the rectangular shape is not formed. A pattern made of a photosensitive resin (second pattern 2) was obtained.

  Next, the sample on which the pattern was formed on the wafer was put in a sealed container and left at room temperature in an atmosphere of PGMEA (propylene glycol monoethyl acetate) which is a solvent for the non-photosensitive resin. When the standing time was changed from 0 minute to 60 minutes, it was confirmed that the longer the standing time, the rounder the pattern shape and the narrower the opening. Thereafter, the non-photosensitive resin was cured by heating at 180 ° C. for 60 minutes, but almost no change in pattern shape was observed during the heat curing.

  Furthermore, a desired stress relaxation wiring can be formed by forming a wiring and an upper resin layer on a non-photosensitive resin having a rounded pattern.

(Example 2)
A polyimide non-photosensitive resin sheet (dry film in semi-cured state, manufactured by Ube Industries, trade name: Upilex Coverlay) is used as the material to be patterned, and the non-photosensitive resin sheet is pasted with a vacuum laminator. A pattern (second pattern 2) made of a non-photosensitive resin was formed in the same manner as in Example 1 except that the layer 2 made of the material to be patterned was formed.

Example 3
A pattern made of a non-photosensitive resin in the same manner as in Example 1 except that a cutter blade was used to remove the non-photosensitive resin remaining on the plating pattern as the first pattern 1 and the ashing step was omitted (second pattern) Pattern 2) was formed. A good pattern similar to that of Example 1 was obtained.

Example 4
In Example 1, a fluorine-based coating was prepared by spraying a fluorine-based coating agent before peeling off the plating resist. After stripping the plating resist, if the same non-photosensitive resin as in Example 1 that is the material to be patterned is applied, the non-photosensitive resin does not adhere to the upper part of the plating pattern, and the plating layer can be etched without ashing Met.

(Example 5)
A first pattern 1 made of a plating layer was formed in the same manner as in Example 1 except that the glass substrate was used as the substrate 3 and the mask pattern was formed with openings at equal intervals. A pattern (second pattern 2) is formed using an acrylate-based transparent non-photosensitive resin (polymethyl methacrylate) as a pattern material, and methyl ethyl ketone as a vaporizing solvent in a solvent atmosphere (room temperature, 0 to 60 minutes) When the pattern was rounded using, a round pattern (microlens) having a desired shape was obtained. After heat curing, the thin film made of acrylate-based transparent non-photosensitive resin could be peeled off from the glass substrate, and a thin film in which microlenses were arranged could be produced.

(Example 6)
A pattern (second pattern 2) was formed in the same manner as in Example 1 except that a photosensitive resin (manufactured by Bantico, trade name: Bantico Provimer) was used instead of the non-photosensitive resin. A good pattern was obtained by etching away the plating pattern.

(Example 7)
As in Example 1, a plating pattern (first pattern 1) serving as a mold was formed. An inorganic material solution consisting of a mixed solution (butanol-based solvent) of glass powder (manufactured by Nippon Denki Glass) and alumina powder (manufactured by Ray Nozzle) is applied onto the substrate on which the plating pattern is formed by a bar coater, and 120 ° C. for 30 minutes. Dried. When observed with an optical microscope, an inorganic material layer (layer 2 made of a material to be patterned) was formed in such a manner that the inorganic material was in contact with the side surface of the plating layer. No inorganic material layer remained on the top of the plating. When the wafer on which the plating pattern and the inorganic material layer were formed was immersed in a copper etching solution and a titanium etching solution, the plating pattern was opened, and a rectangular pattern (second pattern 2) was obtained.

  A sample with a pattern formed on the wafer was placed in a sealed container and allowed to stand in an atmosphere of a butanol solvent (60 ° C., 0 to 60 minutes), which is a solvent for inorganic materials. It was confirmed that the shape of the pattern (second pattern 2) was rounded and the opening was narrowed with the standing time. When it was transformed into a predetermined shape, it was taken out from the sealed container and baked at 800 ° C. for 60 minutes. As a result, a round pattern of glass ceramic was obtained.

(Example 8)
An aqueous solution of silica alkoxide was used as the inorganic material to be patterned, poured into a plating pattern (first pattern 1) produced in the same manner as in Example 5, and dried. The silica alkoxide aqueous solution on the plating pattern was naturally repelled, and an inorganic film (layer 2 made of the material to be patterned) was generated only in the concave portion of the plating pattern. When the silica alkoxide was baked, a colorless and transparent glass thin film was obtained. After repeating this operation 30 times, when the plating pattern was removed by etching, a glass periodic structure (second pattern 2) was obtained, and when light was transmitted, it was confirmed that it acted as a diffraction structure.

(Comparative Example 1)
As in Example 1, after forming a non-photosensitive resin rectangular pattern (second pattern 2) using the plating pattern (first pattern 1) as a mold, it was rapidly heated to 180 ° C. for the purpose of rounding by heating. Although heated, the rectangular pattern remained in its initial shape and was not deformed.

(Comparative Example 2)
The same photosensitive resin as in Example 6 was used, and pattern formation was attempted by normal exposure and development processes. However, since the film thickness was thick, the side surface of the opening portion was inclined and the wafer bottom could not be securely opened.

  The pattern forming method made of the non-photosensitive resin or the like of the present invention enables high-precision patterning even in a thick film, and the deformation method of the resin pattern or the like of the present invention uses a wide range of organic materials and inorganic materials. Therefore, it can be used for a stress relaxation structure on an LSI using a non-photosensitive resin having low elasticity and high elongation, a microlens having high strength and high transparency, and the like.

It is a process figure which shows an example of the pattern formation method of this invention. It is a process figure which shows another example of the pattern formation method of this invention. It is a process figure which shows another example of the pattern formation method of this invention. It is a process figure which shows another example of the pattern formation method of this invention. It is a process figure which shows another example of the pattern formation method of this invention. It is explanatory drawing of the pattern formation method including the process of changing the pattern formed by this invention into the desired shape. It is process drawing which shows an example of the preparation methods of the thin film of this invention. It is process drawing which shows another example of the preparation methods of the thin film of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 1st pattern 1a, 1b, 1c, 1d Plating pattern 2 2nd pattern (layer which consists of pattern material)
3 Substrate 4, 5 Opening 6 Coating 7 Plating resist 11, 12 Thin film 21 Top edge 22 Bottom edge 61, 71, 81 Recess 62, 82 Opening 83 Other layers

Claims (10)

  A first pattern is formed on the substrate, a layer made of a pattern material is formed in an opening of the first pattern, and then the first pattern is removed to form a second pattern made of the pattern material A pattern forming method comprising forming a pattern.   The pattern forming method according to claim 1, wherein the first pattern is a pattern made of a metal or a photosensitive resin.   The pattern forming method according to claim 1, wherein the pattern material is an organic material or an inorganic material.   The pattern forming method according to claim 1, wherein the layer made of the pattern material is formed by applying a liquid pattern material.   The pattern formation according to any one of claims 1 to 3, wherein the layer made of the material to be patterned is formed by sticking a film-like material to be patterned on the first pattern. Method.   The layer made of the material to be patterned is formed by applying or pasting the material to be patterned on the first pattern after forming a film that repels the material to be patterned on the first pattern. The pattern formation method of any one of Claims 1-3 characterized by the above-mentioned.   After the layer made of the pattern material is applied or pasted on the first pattern, the upper portion of the first pattern is exposed by mechanical or chemical treatment, and then the first pattern is exposed. It forms by removing one pattern, The pattern formation method of any one of Claims 1-6 characterized by the above-mentioned.   After the second pattern made of the pattern material is formed by the pattern forming method according to any one of claims 1 to 7, the second pattern is placed in a solvent atmosphere that can deform the pattern material. A pattern forming method, wherein the pattern is deformed.   A pattern forming method characterized in that the rectangular pattern is deformed by placing the substrate after forming the rectangular pattern in a solvent atmosphere capable of deforming the rectangular pattern.   After forming a pattern on a board | substrate with the pattern formation method of any one of Claims 1-9, the said board | substrate is removed or the layer and board | substrate which have the said pattern are isolate | separated, and the thin film which has the said pattern A method for manufacturing a thin film, characterized by comprising:

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