JPH10158849A - Production of pattern forming body - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a process for producing a pattern forming body which is arranged with plural approximately spherical member or approximately hemispherical members in a pattern form on a substrate. SOLUTION: The pattern forming body which is arranged with at least the plural approximately spherical members approximately hemispherical members 3 in the pattern form on the substrate 1 is produced. The material of the substrate 1 is formed of a reaction initiation material which acts as a catalyst for an electroless plating reaction. The surface of the substrate is otherwise provided with a reaction initiation material layer 1b and further, the surface thereof has plural apertures 1a and a non-reaction initiation material layer 4 which does not act as the catalyst for an electroless plating reaction is formed thereon in correspondence to the patterns. Plating films are then respectively grown by an electroless plating method in the respective apertures 1a, by which the approximately spherical members or approximately hemispherical members 3 are formed.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a pattern formed body in which at least a plurality of substantially spherical members or substantially hemispherical members are arranged in a pattern on a substrate.

[0002]

2. Description of the Related Art Microfabrication technology has progressed rapidly, and the main focus has now shifted to the development of memory fabrication technology on the order of 0.1 μm. However, the pattern formed body for memory fabrication has a rectangular cross section or trapezoidal shape. Most have a cross section. However, this is not to say that a spherical (hemispherical) or approximately spherical (substantially hemispherical) pattern forming body having a circular or approximately circular cross section is not required. Such a pattern forming body is expected to be used as a light scatterer.

Some optical devices have a light scattering member provided in the optical system, and the light scattering member is generally manufactured by treating the surface of a substrate with sand blast or the like. Further, there is a device called a dust inspection device for inspecting the size and the number of dust existing on a substrate member such as a photomask or a silicon wafer used in a manufacturing process of a semiconductor element or the like. , A photomask, a silicon wafer, and the like) to detect minute dust on the sample surface and its size from the scattering intensity and scattering directivity when light is irradiated.

[0004] The photomultiplier of this dust inspection apparatus requires an initial setting so as to have a constant sensitivity and an evaluation of fluctuation over time. To adjust the sensitivity, a light scatterer having a constant particle diameter is adjusted to an appropriate density. A light scattering plate for calibration is used which is distributed such that This light scattering plate preferably exhibits the same scattering characteristics as the dust to be inspected. For example, a plurality of fine particles (light scattering bodies) having the same size as the dust and having relatively isotropic scattering characteristics are arranged on the substrate. Is preferred.

In view of the above demands, a review of existing microfabrication techniques reveals that dry etching and wet etching can be broadly classified as methods for producing fine patterns having a pattern size of several tens of nanometers or more. An etching method can be given. Dry etching includes reactive ion etching (RIE), ion beam etching, and focus ion beam etching (FI).
B) method, laser processing method and the like.

In wet etching, etching is performed by immersing a target member in an etchant suitable for the material of the member to be etched. Here, the RIE method is taken as an example, and the fine pattern processing method will be described with reference to FIG. First, a layer 13 to be processed is formed on the substrate 11, and a resist pattern 14 is further formed thereon.
(A)). It is the same as in the present invention that the resist material is selectively used for EB, ultraviolet exposure and the like depending on the pattern forming method.

After that, the resist pattern 14 is transferred to the layer 13 to be processed (FIG. 4B). The transfer method is RIE
Method, an ion beam etching method and the like are generally used. This transfer method is desirably selected in consideration of the material of the layer to be processed. Thereafter, the resist pattern 14 used as a mask is peeled off to complete a fine pattern (FIG. 4C).

Here, in order to control the upper shape of the pattern to be processed in the pattern formation by the RIE method, it is necessary to optimize the mask shape or the mask thickness to a certain condition. In addition, the mask thickness in the ordinary microfabrication is set such that the mask remains at the end of etching from the etching selectivity at the time of pattern transfer to the lower layer (for example, FIG. 4B). If the thickness is less than the thickness that can be assumed from the etching selectivity, the etching selectivity becomes insufficient, and the lower layer pattern is gradually cut from the edge portion. When etching is performed under these conditions, a pattern having a trapezoidal cross section or a triangular cross section is obtained.

In the case of wet etching, RIE is also used.
It is performed in the same manner as the processing by the method, but since the pattern transfer is isotropic etching, unlike the case of the RIE method, the pattern to be processed is tapered, and the formed pattern is T-type or I-type. (FIG. 4D).

[0010]

As described above, in the pattern formation by the RIE method, the pattern of the cross-sectional shape can be obtained by controlling the mask shape, the mask thickness, and the like. In order to form a pattern having a hemispherical shape, it is necessary to make the mask shape approximately hemispherical.

However, at present, no report has been made on a method for forming and controlling a mask pattern having a substantially hemispherical shape. Considering the transfer characteristics of both the RIE method and the ion beam etching method, it is considered that the mask pattern shape will not be transferred linearly as it is, in which case it is necessary to optimize the mask shape. , Its control becomes increasingly difficult.

As described above, it is possible to produce a pattern having a triangular cross section or a polygonal cross section by the existing microfabrication technique, but there is no report on a technique for producing a roughly spherical or roughly hemispherical pattern. . In addition, for example, when a member of a light scatterer is required, the shape of the light scatterer is preferably a desired shape. For example, when isotropic scattering characteristics are required, the shape of the light scatterer may be spherical, Spherical,
Must be hemispherical or approximately hemispherical.

If a pattern composed of such a spherical, roughly spherical, hemispherical, or roughly hemispherical light scatterer is arranged on a substrate, it becomes an extremely good light scattering plate (member) and can be used for various optical devices and the like. Can be used. Such a light scattering plate (member) is particularly a dust inspection apparatus for inspecting the size and number of dust existing on a substrate member such as a photomask or a silicon wafer used in a manufacturing process of a semiconductor element or the like described in the above-mentioned conventional technique. It is most suitable as a light scattering plate for calibration for adjusting the sensitivity and the like in.

In spite of the various uses as described above, it is a serious problem that a technique for forming a pattern including a spherical, approximately spherical, hemispherical, or approximately hemispherical member has not been established. In addition, when a pattern made of a spherical, approximately spherical, hemispherical, or approximately hemispherical member is formed on a substrate for the above-described purpose, the pattern size and the layout are further manufactured to a desired size or layout. Needless to say, it is more preferable to use a method that can be controlled as much as possible.

As described above, there is a strong demand for the development of a method for producing a pattern comprising a spherical, approximately spherical, hemispherical, or approximately hemispherical member. The present invention has been made in view of the above problems and needs, and has a plurality of spherical shapes on a substrate.
Provided is a method for manufacturing a pattern forming body in which hemispherical, approximately spherical, or approximately hemispherical members (hereinafter, referred to as approximately spherical members or approximately hemispherical members) are arranged in a pattern. It is intended to be.

[0016]

Therefore, the present invention firstly provides a method for producing a pattern formed body in which at least a plurality of substantially spherical members or substantially hemispherical members are arranged in a pattern on a substrate, The material of the substrate may be a reaction starting material serving as a catalyst for the electroless plating reaction, or a reaction starting material layer may be provided on the surface of the substrate, and the surface may have a plurality of openings to provide a catalyst for the electroless plating reaction. Forming a non-reaction initiating material layer corresponding to the pattern, growing a plating film in each opening by an electroless plating method to form the approximately spherical member or the approximately hemispherical member. A method for producing a patterned body (Claim 1) "is provided.

The present invention also provides a method of manufacturing a semiconductor device, wherein the material of the plating film is Ag, Au, Co, Cu, Fe, Ir, Ni, O
s, Pd, Pt, Rh, or Ru; and a manufacturing method according to claim 1 (claim 2). In addition, the present invention has a third feature that "a substantially spherical member or a substantially hemispherical member is formed in the opening by making the shape of the opening circular or substantially circular.
Or 2) (claim 3).

[0018] Fourth, the present invention provides a method according to claim 3, wherein the size of the opening is smaller than the size of the substantially spherical member or the substantially hemispherical member. )"I will provide a. Further, the present invention fifthly provides that "the non-reaction starting material layer is formed of one or more layers, and at least one layer is formed of a resist material or a material containing silicon oxide as a main component. ~ 4
The manufacturing method described in claim 5 is provided.

The present invention is also directed to a sixth aspect of the present invention in which "the reaction initiating material layer is formed of one or more layers, or the substrate is made of a reaction initiating material, and at least Pd, Co, Fe, Ir is used as the reaction initiating material. , Ni, Os, Pt, Rh, or Ru is provided. In addition, the present invention seventh, "the size of the approximately spherical member or approximately hemispherical member,
The method according to claim 1, wherein the size is controlled by at least one of the size of the opening, the amount of plating current, the immersion time of the plating solution, and the composition of the plating solution. provide.

[0020]

According to the method of manufacturing a pattern-formed body according to the present invention, the material of the substrate is used as a reaction starting material serving as a catalyst for an electroless plating reaction, or the reaction starting material is provided on the surface of the substrate. A layer is provided, a non-reaction starting material layer having a plurality of openings on its surface and not serving as a catalyst for the electroless plating reaction is formed in accordance with the pattern, and a plating film is formed on each opening by an electroless plating method. By growing each, a substantially spherical member or a substantially hemispherical member is formed.

That is, according to the method of manufacturing a pattern forming body according to the present invention, the plurality of openings are formed in a desired pattern, and a substantially spherical member or a substantially hemispherical member is formed in each of the openings by electroless plating. Since it is formed, it is possible to provide a roughly spherical member or a roughly hemispherical member on a substrate in a desired number, distribution, size, shape, and as a result, a plurality of roughly spherical members or roughly hemispherical members are formed on the substrate. It is possible to manufacture a pattern formed body in which members are arranged in a desired pattern (claim 1).

As long as at least the surface of the substrate according to the present invention is made of the above-mentioned reaction-initiating substance, a plating film can be easily grown by electroless plating. At this time, the entire substrate may be composed of a reaction initiating substance, or a reaction initiating substance layer may be formed on the surface of the substrate. FIG. 1 shows a schematic cross section of a pattern formed body (one example) according to the present invention, and FIG. 2 shows a partial process of a method (one example) of manufacturing a pattern formed body according to the present invention. 1 and 2, a part of the pattern forming body is enlarged and a cross section is shown.

First, a reaction starting material layer 1b serving as a catalyst for an electroless plating reaction is formed on a substrate 1 (FIG. 2A), and a non-reaction starting material layer 4 is formed thereon in a pattern (FIG. 2A). 2 (b)). Further, a substantially spherical member or a substantially hemispherical member 3 is formed by growing a plating film on the exposed portion 1a (opening) of the substrate 1 by electroless plating (FIG. 2C).

Then, the non-reaction-initiating substance layer 4 is removed by dissolution or peeling to complete a pattern formed body in which a plurality of substantially spherical members or substantially hemispherical members are arranged in a desired pattern on the substrate (FIG. 2 (d)). As described above, the approximately spherical member or the approximately hemispherical member according to the present invention is formed by the electroless plating method, and the formation (size and shape) of the approximately spherical member or the approximately hemispherical member by the electroless plating method is controlled. In order to perform the process efficiently, the material of the plating film should be Ag, Au, Co,
It is preferable to use Cu, Fe, Ir, Ni, Os, Pd, Pt, Rh, or Ru (claim 2).

The substantially spherical member or the substantially hemispherical member according to the present invention can be easily formed if the shape of the opening is circular or approximately circular. The substantially spherical member or the substantially hemispherical member according to the present invention is formed in each opening by an electroless plating method. At this time, in each opening, the plating film has a thickness equal to the thickness of the non-reaction starting material layer 4. 2C, the substantially spherical member or the substantially hemispherical member 3 can be easily formed in each opening by further growing isotropically as shown in FIG. 2C. .

At this time, since the roughly spherical member or the roughly hemispherical member 3 is larger than the opening 1a of the non-reaction starting material layer 4, the size of the opening 1a is a desired value of the roughly spherical member or the roughly hemispherical member 3. It is preferable to make it smaller than the size.
That is, it is preferable that the size of the opening is smaller than the size of the member so that a substantially spherical member or a substantially hemispherical member is easily formed in each opening (claim 4).

In the present invention, the non-reaction-initiating substance layer is preferably formed of one or more layers, and at least one layer is preferably formed of a resist material or a material containing silicon oxide as a main component. The non-reaction-initiating substance layer according to the present invention may be a single layer, or may be composed of a plurality of layers so as to facilitate the pattern formation of the openings.

Preferably, at least one of the layers constituting the non-reaction-initiating substance layer is formed of a resist material, since an opening pattern can be easily formed by a lithography process. Alternatively, it is preferable that at least one of the layers constituting the non-reaction starting material layer is formed of a material containing silicon oxide as a main component, because an opening pattern can be easily formed by an etching process or the like (claim 5).

According to the fifth aspect of the invention, the position, size and shape of the opening can be easily controlled, and furthermore, since the approximately spherical member or the approximately hemispherical member is formed only in the opening, the approximately spherical member is formed. The number, distribution (position and density), size and shape of the members or approximately hemispherical members can be easily controlled. In the present invention, it is preferable that the reaction starting material layer is formed of one or more layers, and that the reaction starting material layer is formed of at least Pd, Co, Fe, Ir, Ni, Os, Pt, Rh, or Ru ( Claim 6).

The reaction initiating substance layer according to the present invention may be a single layer, or may be composed of a plurality of layers including a layer for improving the adhesion to the substrate. Further, the reaction starting material layer is formed of one or a plurality of layers, or the substrate is made of a reaction starting material, and at least Pd, Co, Fe, Ir, Ni, Os, Pt, Rh,
Alternatively, it is preferable to use Ru because the plating film (3) grows easily (claim 6).

According to the present invention, the size of the substantially spherical member or the substantially hemispherical member can be easily controlled. For example, a member having a desired size can be obtained by controlling at least one of the size (or area) of the opening, the amount of plating current, the immersion time of the plating solution, and the composition of the plating solution. ). In addition, the size of the approximately spherical member or the approximately hemispherical member largely depends on the plating solution immersion time and / or the plating solution composition.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples.

[0033]

Embodiment 1 FIG. 2 shows some steps of a method of manufacturing a pattern forming body according to the present embodiment. In FIG. 2, a part of the pattern forming body is enlarged and its cross section is shown.
First, a reaction starting material layer 1b serving as a catalyst for an electroless plating reaction is formed on a substrate 1 made of quartz glass having a size of 5 inches.
A thin film layer of Pt was formed by a sputtering method. Further, after applying a resist 4 'on the surface of the Pt thin film layer, the resist was processed into a pattern by an electron beam drawing process to form a resist pattern 4 (FIG. 2B).

At this time, the resist pattern 4 has a diameter of 0.2
It was formed so that a plurality of circular openings 1a of μm or more were arranged. The resist pattern 4 is a non-reaction starting material layer that does not act as a catalyst for the electroless plating reaction. Next, as a result of growing a Ni plating film in each opening 1a of the resist pattern 4 by an electroless plating method using the resist pattern 4 as a stencil mask, a substantially spherical member or a substantially hemispherical member 3 having a diameter of 0.3 μm or more is opened. According to the pattern 1a, a pattern having a desired distribution was formed (FIG. 2C).

At this time, the size of the member 3 is adjusted to a desired size by controlling the plating area (area of the opening), the amount of plating current, the plating time (immersion time in the plating solution), or the composition of the plating solution. On the other hand, a dimensional error of ± 5% or less could be suppressed. As a result, the member 3 having a desired shape (generally spherical or approximately hemispherical) and size could be obtained.
The plating solution used for the electroless plating (plating bath)
Is nickel chloride 30 g / l, sodium hypophosphite 1
0 g / l, aqueous solution of sodium citrate 10 g / l, electroless plating conditions: plating bath pH 4-6, bath temperature 90
° C.

Finally, the resist pattern 4 used as a stencil mask was peeled off and removed with MEK (methyl ethyl ketone), and further washed with an organic solvent or water to complete a pattern formed body (FIG. 2D).

[0037]

[Embodiment 2] FIG. 3 shows some steps of a method of manufacturing a pattern forming body according to the present embodiment. In FIG. 3, a part of the pattern forming body is enlarged and a cross section is shown.
First, a reaction starting material layer 1b serving as a catalyst for an electroless plating reaction is formed on a substrate 1 made of quartz glass having a size of 5 inches.
A thin film layer of Pt was formed by a sputtering method (FIG. 3A).

On the surface of the Pt thin film layer, a silicon oxide thin film layer was formed by a sputtering method as a non-reaction starting material layer 2 'which did not act as a catalyst for the electroless plating reaction, and a resist was applied on the surface of the silicon oxide thin film layer. Thereafter, the resist was processed into a pattern by an electron beam drawing process to form a resist pattern 4 (FIG. 3B). At this time, the resist pattern 4 was formed such that a plurality of circular openings having a diameter of 0.2 μm or more were arranged. Next, the resist pattern 4 was transferred to the silicon oxide thin film layer 2 by a reactive ion etching method to form a pattern of the opening 1a (FIG. 3C).

Further, as a result of growing a Ni plating film in each opening 1a of the silicon oxide thin film layer 2 by an electroless plating method, a substantially spherical member or a substantially hemispherical member 3 having a diameter of 0.5 μm or more has a pattern of the opening 1a. (FIG. 3D). At this time, the size of the member 3 is suppressed to an error of 0.1 μm or less by controlling the plating area (opening area), the amount of plating current, the plating time (immersion time in the plating solution), or the composition of the plating solution. I was able to. As a result, the member 3 having a desired shape (a shape having a part of a sphere or a substantially sphere) and a size could be obtained.

The plating solution used for the electroless plating was nickel chloride 30 g / l, sodium hypophosphite 1
It is an aqueous solution of 0 g / l and 10 g / l of sodium citrate. Electroless plating conditions are plating bath pH 4-6, bath temperature 9
0 ° C. Finally, the silicon oxide thin film layer 2 used as a stencil mask was peeled off by an oxygen ashing method, and further washed with an organic solvent, water or the like to complete a pattern formed body (FIG. 3E).

[0041]

As described above, according to the present invention, it is possible to provide a substantially spherical member or a substantially hemispherical member on a substrate in a desired number, distribution, size, and shape. A pattern formed body in which spherical members or approximately hemispherical members are arranged in a desired pattern can be manufactured with high yield.

Further, according to the present invention, a light scattering plate using a substantially spherical member or a substantially hemispherical member as a light scattering body can be easily manufactured. According to the light scattering plate, substantially isotropic scattering characteristics can be obtained. Further, according to the present invention, since the size and arrangement position of the light scatterer can be easily controlled, a light scatter plate having desired light scatter characteristics can be manufactured with a high yield.

Further, the pattern formed body manufactured according to the present invention can be used as an optical component for controlling a light quantity distribution of an illumination optical system in an optical apparatus.

[Brief description of the drawings]

FIG. 1 is a schematic sectional view of a pattern forming body (one example) according to the present invention.

FIG. 2 is a process diagram illustrating some steps of a method for manufacturing a pattern forming body according to the first embodiment.

FIG. 3 is a process diagram illustrating some steps of a method for manufacturing a pattern forming body according to Example 2.

FIG. 4 is a schematic cross-sectional view of a pattern formed body manufactured by a conventional manufacturing method.

[Description of Signs of Main Parts]

 DESCRIPTION OF SYMBOLS 1 ... Substrate 1a ... Opening 1b ... Reaction initiation material layer 2 ... Patterned non-reaction initiation material layer 2 '... Non-reaction initiation material layer 3 ... Almost spherical member or Hemispherical member 4 ... Patterned resist layer 4 '... Resist layer 11 ... Substrate 13 ... Work layer 13a ... Work pattern (dry etching method) 13b ... Work pattern (Wet etching method) 14 ... patterned resist layer

Claims (7)

[Claims] 1. A method for producing a pattern formed body in which at least a plurality of substantially spherical members or substantially hemispherical members are arranged in a pattern on a substrate, wherein the material of the substrate serves as a catalyst for an electroless plating reaction. A reaction initiating material or a reaction initiating material layer provided on the surface of the substrate, and a non-reaction initiating material layer having a plurality of openings on the surface and not serving as a catalyst for the electroless plating reaction corresponds to the pattern. And forming a substantially spherical member or a substantially hemispherical member by growing a plating film in each opening by an electroless plating method. 2. The material of the plating film is made of Ag, Au, C
o, Cu, Fe, Ir, Ni, Os, Pd, Pt, R
The method according to claim 1, wherein h or Ru is used. 3. The manufacturing method according to claim 1, wherein the shape of the opening is circular or substantially circular, so that a substantially spherical member or a substantially hemispherical member is formed in the opening. 4. The method according to claim 3, wherein the size of the opening is smaller than the size of the substantially spherical member or the substantially hemispherical member. 5. The method according to claim 1, wherein the non-reaction starting material layer is formed of one or more layers, and at least one layer is formed of a resist material or a material containing silicon oxide as a main component. Production method. 6. The reaction initiating material layer is formed of one or more layers, or the substrate is made of a reaction initiating material, and at least Pd, Co, Fe,
6. The method according to claim 1, wherein Ir, Ni, Os, Pt, Rh, or Ru is used. 7. Controlling the size of the substantially spherical member or the substantially hemispherical member by at least one of a size of the opening, a current amount of plating, a plating solution immersion time, and a plating solution composition. The method according to any one of claims 1 to 6, wherein: