JP2005136002A - Mask for photo-electrochemical etching, its forming method and manufacturing method for semiconductor device using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a mask which can be used for a photo-electrochemical etching, can be worked finely, and has a resistance against an acid and an alkali, to provide a method for forming the mask and a manufacturing method for a semiconductor device using the mask for the photo-electrochemical etching. <P>SOLUTION: The mask 130 for the photo-electrochemical etching to a III nitride semiconductor 106 is composed of one kind or two kinds or more of mask materials selected from a mask material group consisting of silicon nitride, aluminum nitride, silicon oxide, aluminum oxide, silicon oxynitride, and aluminum oxynitride. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a photoelectrochemical etching mask, a method for forming a photoelectrochemical etching mask, and a method for manufacturing a semiconductor device using the photoelectrochemical etching mask.

  In a high electron mobility transistor (HEMT), a recessed gate structure is used to realize high amplification characteristics and high frequency characteristics. The HEMT is widely used in GaAs-based and InP-based group III-V semiconductor devices. A group III nitride semiconductor which is a group III-V semiconductor can be used as a HEMT. However, in reality, the recess gate structure is not often used in the group III nitride semiconductor device. This is because the group III nitride semiconductor is a chemically stable material, so that wet etching is difficult.

  As a method for etching a group III nitride semiconductor, a dry etching method using silicon oxide or the like as a mask material (for example, see Patent Document 1) or a photoelectrochemical etching method has been proposed (for example, Patent Document 2 or Non-patent document 1).

In particular, by applying this photoelectrochemical etching to recess etching, it is expected that recess etching with a large area and high uniformity can be performed at low cost (for example, see Non-Patent Document 2).
Japanese Patent No. 3254436 “Method for manufacturing etching mask in gallium nitride compound semiconductor” (paragraphs 0008 to 0010) JP 11-229199 A “Nitride Material Etching Method” (Claim 1) C. Youthsey et al., “Smooth n-type GaN surfaces by photoenhanced wet etching” Appl. Phys. Lett. 72, pp. 560-562, 1998 Jae-Seung LEE et al., “Photo-Electrochemical Gate Recessed Etching for the Fabrication of AlGaN / GaN Heterostructure Field Effect Transistor” Jpn. J. et al. Appl. Phys. 40, pp. L198-L200, 2001

  However, in the dry etching method, the vicinity of the semiconductor substrate surface may be damaged by plasma ions or the like.

  When the photoelectrochemical etching method is performed, a conventionally used mask for photoelectrochemical etching (hereinafter simply referred to as a mask) using a metal, a photoresist or a wax must be removed after the etching, and the removal is performed. There is a concern that the surface of the semiconductor is contaminated during the work.

  Furthermore, masks made of metal, photoresist, or wax each have the following practical problems. The metal mask cannot be used when photoelectrochemical etching is performed after the electrode is formed. Since the wax mask cannot use photolithography, a fine pattern cannot be etched. The photoresist mask has low resistance to hot ammonia water, acid, and the like used when removing a large amount of oxide deposited on the etching surface.

  In addition, it is unclear whether a mask material used in conventional wet etching or dry etching of another semiconductor can be used in photoelectrochemical etching.

  Accordingly, an object of the present invention is to provide a photoelectrochemical etching mask that can be used for photoelectrochemical etching, can be finely processed, and is resistant to acids and alkalis, and a method for forming the same. It is another object of the present invention to provide a method for manufacturing a semiconductor device using the photoelectrochemical etching mask.

  According to the photoelectrochemical etching mask for a group III nitride semiconductor of the present invention, the mask is selected from a mask material group consisting of silicon nitride, aluminum nitride, silicon oxide, aluminum oxide, silicon oxynitride, and aluminum oxynitride. In addition, it is composed of one or more kinds of mask materials.

  The method for forming a photoelectrochemical etching mask of the present invention includes the following steps. In the first step, one or two kinds selected from the mask material group consisting of silicon nitride, aluminum nitride, silicon oxide, aluminum oxide, silicon oxynitride, and aluminum oxynitride are formed on the entire upper surface of the group III nitride semiconductor substrate. A preliminary mask layer made of the above mask material is formed. In the second step, a photoresist layer is formed on the preliminary mask layer formed in the first step, and then an opening is patterned in the photoresist layer to form a photoresist pattern. In the third step, the region of the preliminary mask layer exposed at the opening of the photoresist pattern is removed by etching to form the opening. In the fourth step, the photoresist pattern is removed.

  The method for manufacturing a group III nitride semiconductor device of the present invention includes the following steps. In the first step, a source electrode and a drain electrode are formed on the surface of the group III nitride semiconductor substrate. In the second step, a mask material group made of silicon nitride, aluminum nitride, silicon oxide, aluminum oxide, silicon oxynitride, and aluminum oxynitride is formed on the entire upper surface of the group III nitride semiconductor substrate on which the source electrode and the drain electrode are formed. A preliminary mask layer made of one or more selected mask materials is formed. In the third step, a photoresist layer is formed on the preliminary mask layer formed in the second step, and then an opening is patterned in the photoresist layer to form a photoresist pattern. In the fourth step, the region of the preliminary mask layer exposed at the opening of the photoresist pattern is removed by etching to form the opening. In the fifth step, the photoresist pattern is removed to form a photoelectrochemical etching mask. In the sixth step, the group III nitride semiconductor substrate is photoelectrochemically etched using the photoelectrochemical etching mask formed in the steps up to the fifth step. In the seventh step, a gate electrode is formed in a portion etched by photoelectrochemical etching.

  According to the photoelectrochemical etching mask of the present invention, the etching mask is one or two selected from the mask material group consisting of silicon nitride, aluminum nitride, silicon oxide, aluminum oxide, silicon oxynitride, and aluminum oxynitride. The mask is made of a mask material of more than seeds. Since the mask material constituting this mask is usually used as a passivation film or an interlayer insulating film in a semiconductor device, in this case, it can be used as a passivation film or an interlayer insulating film without removing the etching mask. it can.

When using these materials, compared to conventional metal masks, wax masks, photoresist masks, etc.
(1) Sufficient resistance to the etchant.
(2) The oxide stacked on the etching surface can be easily removed.
(3) After etching, the mask itself can be used as a surface protective film.
And so on.

  Further, when the dry etching method is used as an etching method, the vicinity of the surface of the semiconductor substrate may be damaged by plasma ions. However, if the photoelectrochemical etching method is used, there is no risk of damage by plasma ions.

  According to the method for forming a mask for photoelectrochemical etching of the present invention, since the mask for photoelectrochemical etching is formed using the mask material described above, the mask itself is used as a passivation film or an interlayer insulating film of a semiconductor device. Can be used as Therefore, the mask removal step can be omitted finally.

  According to the method for manufacturing a group III nitride semiconductor device of the present invention, since the mask is formed using the above-described method for forming a mask for photoelectrochemical etching, the mask itself is similarly used as a passivation film for a semiconductor device. It can also be used as an interlayer insulating film. For this reason, the process of removing this mask and the process of forming a new passivation film for the semiconductor device can be omitted.

  Further, when the dry etching method is used as the etching method, the vicinity of the surface of the semiconductor substrate may be damaged by plasma ions. However, according to the method for manufacturing a semiconductor device of the present invention, such a damage is caused. No fear of receiving.

  Hereinafter, embodiments of the present invention will be described with reference to the drawings. However, the shape, size, and arrangement relationship are merely schematically shown to the extent that the present invention can be understood. In the following, a preferred configuration example of the present invention will be described. However, the composition (material) and numerical conditions of each configuration are merely preferred examples. Therefore, the present invention is not limited to the following embodiment.

(Mask for etching)
The details of the photoelectrochemical etching will be described later, but the photoelectrochemical etching is performed by irradiating a semiconductor to be etched placed in a required etchant with light having a short wavelength having energy larger than the band gap energy. This is done by the semiconductor losing electrons and decomposing.

  The etching resistant mask used in this photoelectrochemical etching is referred to as a photoelectrochemical etching mask. The photoelectrochemical etching mask is formed of the following single mask material or a mixed material of a plurality of mask materials. Examples of the mask material include silicon nitride, aluminum nitride, silicon oxide, aluminum oxide, silicon oxynitride, and aluminum oxynitride. Therefore, the photoelectrochemical etching mask is formed with one kind of mask material selected from these mask material groups, or two or more kinds of masks selected from these mask material groups, that is, a plurality of mask materials are selected. A mask material (referred to as a mixed mask material) in which seed mask materials are mixed is formed. Mask materials belonging to this mask material group are conventionally used in semiconductor devices as a passivation film and an interlayer insulating film, respectively. In addition, it has resistance to an etchant used in photoelectrochemical etching.

(Method for forming etching mask)
An embodiment of a method for forming a photoelectrochemical etching mask will be described with reference to FIGS. FIGS. 1A to 1E are process diagrams for forming a mask for photoelectrochemical etching. In addition, each figure has shown the cut surface of the cross section of the structure obtained in the formation process step. In this embodiment, a GaN substrate is used as a group III nitride semiconductor, and a mask is formed as an example when photoelectrochemical etching is performed on the substrate after a required electrode is formed on the substrate. To do.

  First, ohmic electrodes 22 and 24 are formed by vapor-depositing titanium on the surface of the GaN substrate 10 which is a group III nitride semiconductor. In the illustrated configuration example, the two electrodes 22 and 24 are formed apart from each other. The electrodes 22 and 24 are used as a drain electrode and a source electrode, for example, when a field effect transistor (FET) is manufactured from a group III nitride semiconductor. Here, another group III nitride semiconductor may be used instead of GaN. In addition to titanium, an ohmic material such as aluminum, nickel, or indium can be used as the ohmic electrode (FIG. 1A).

  Next, a preliminary mask layer 30 is formed on the entire upper surface of the GaN substrate 10 on which the ohmic electrodes 22 and 24 are formed (FIG. 1B). In this configuration example, the preliminary mask layer 30 is formed as a silicon nitride film by a known plasma CVD method using silicon nitride as a mask material. Here, instead of using silicon nitride as the mask material, one kind of mask material selected from the mask material group consisting of aluminum nitride, silicon oxide, aluminum oxide, silicon oxynitride, and aluminum oxynitride may be used, Alternatively, two or more types of mask materials consisting of silicon nitride, aluminum nitride, silicon oxide, aluminum oxide, silicon oxynitride, and aluminum oxynitride, that is, a plurality of types of mask materials may be selected and used.

  Next, a photoresist pattern 40 is formed on the preliminary mask layer 30. In this case, first, a photoresist made of an organic resin is applied on the preliminary mask layer 30 to form a photoresist layer. Thereafter, patterning is performed by a well-known photolithography method, and openings 40a and 40b are provided in the planned etching locations of the GaN substrate 10 to form a photoresist pattern 40 (FIG. 1C). In this configuration example, the planned etching location of the GaN substrate 10 is set in a substrate region that is out of the ohmic electrodes 22 and 24. Accordingly, the opening 40a is formed in a portion of the photoresist layer that is off from directly above the ohmic electrodes 22 and 24, and the surface of the preliminary mask layer 30 is exposed in the openings 40a and 40b.

Next, the region portion of the preliminary mask layer 30 which is a silicon nitride film exposed in the openings 40a and 40b of the photoresist pattern is removed by etching to form a photoelectrochemical etching mask 50 (FIG. 1D). )). Here, reactive ion etching (RIE) using CF ₄ gas or hydrofluoric acid is used by using the photoresist pattern 40 provided by the process described with reference to FIG. 1C as an etching mask. The exposed portion of the preliminary mask layer 30 is removed to the surface of the GaN substrate 10 by wet etching or the like used. Openings formed in the preliminary mask layer 30 by this etching are indicated by 30a and 30b. Since GaN and other group III nitride semiconductors are chemically stable substances, they are not etched by wet etching, and etching of the silicon nitride film 30 stops at the surface of the GaN substrate 10. When performing RIE, the gas used for RIE can be selected according to a mask material.

  Next, the photoresist pattern 40 is removed. By removing the photoresist pattern 40, the photoelectrochemical etching mask 50 in which the openings 30a and 30b are formed in the preliminary mask layer 30 remains (FIG. 1E). Through the above steps, a photoelectrochemical etching mask 50 is formed on the group III nitride semiconductor.

  After the formation of the photoelectrochemical etching mask 50, an ohmic metal electrode 60 is formed by vapor deposition or the like as an extraction lead electrode (FIG. 1F). Thereafter, photoelectrochemical etching is performed on the underlying GaN substrate 10.

  The photoelectrochemical etching mask thus formed is formed of a material used as a passivation film or an interlayer insulating film of a semiconductor device, such as silicon nitride. These mask materials have (1) sufficient resistance against an etchant compared with conventional metal masks, wax masks, photoresist masks, etc., and (2) removal of an oxide film laminated on an etching surface. It is easy, and (3) has an advantage that the mask itself can be used as a surface protective film after etching.

(Method of manufacturing group III nitride semiconductor device)
Next, with reference to FIGS. 2 (A) -2 (D) and FIGS. 3 (A) -3 (C), a method for manufacturing a group III nitride semiconductor device will be described. 2 (A) -2 (D) and FIGS. 3 (A) -3 (C) show an embodiment of a method for manufacturing a group III nitride semiconductor device when GaN is used as a group III nitride semiconductor. It is process drawing for demonstrating each.

  First, a group III nitride semiconductor substrate (GaN substrate) 110 is formed by sequentially laminating GaN 102, AlGaN 104, and GaN 106 on the Si substrate 100 (FIG. 2A). Instead of the Si substrate 100, sapphire, SiC, or the like may be used.

  A source electrode 122 and a drain electrode 124 are formed on the GaN substrate 110 as ohmic electrodes (FIG. 2B). The ohmic electrode material and the formation method are the same as those described in the first step in the above-described etching mask formation method.

  A preliminary mask layer (not shown) is temporarily formed on the entire upper surface of the GaN substrate 110 on which the source electrode 122 and the drain electrode 124 are formed by a known plasma CVD method (see FIG. 1B). As this preliminary mask layer, a silicon nitride film using silicon nitride as a mask material is formed. Here, instead of using silicon nitride as the mask material, one kind of mask material selected from the mask material group consisting of aluminum nitride, silicon oxide, aluminum oxide, silicon oxynitride, and aluminum oxynitride may be used, Alternatively, two or more types of mask materials consisting of silicon nitride, aluminum nitride, silicon oxide, aluminum oxide, silicon oxynitride, and aluminum oxynitride, that is, a plurality of types of mask materials may be selected and used. Further, a photoresist layer (not shown) made of an organic resin is applied and formed on the preliminary mask layer. Thereafter, the photoresist layer is patterned by a known photolithography method to form a photoresist pattern. This photoresist pattern has an opening (not shown) in the same manner as described with reference to FIG. This opening is provided at a planned etching location of the GaN substrate 110.

Next, the region of the preliminary mask layer exposed at the opening of the photoresist pattern is etched away to the surface of the GaN substrate 110 by RIE using CF ₄ gas, wet etching using hydrofluoric acid, or the like. Thereafter, by removing the photoresist pattern, a preliminary mask layer is formed as a photoelectrochemical etching mask 130 (FIG. 2C). In the drawing, an opening provided in the photoelectrochemical etching mask 130 is indicated by 130a. Since GaN and other group III nitride semiconductors are chemically stable substances, they are not etched by wet etching, and etching of the silicon nitride film stops at the surface of the GaN substrate 110. When performing RIE, the kind of gas used for RIE can be selected according to mask material. A structure having two electrodes 122 and 124 on the substrate 110 and a photoelectrochemical etching mask 130 which is a silicon nitride film in which an opening 130 a is formed is referred to as an etched structure 112.

  Next, photoelectrochemical etching for forming a recess in the GaN 106 is performed on the structure 112 to be etched. FIG. 4 schematically shows the configuration of an apparatus used for photoelectrochemical etching. A solution obtained by dissolving potassium hydroxide, sodium hydroxide, hydrochloric acid or the like in water, glycol or the like is used as the etchant 202 in the photoelectrochemical etching container 200 such as a beaker. A support 204 is provided in the container 200. A structure to be etched 112 including a silicon nitride film as a photoelectrochemical etching mask 130 on the GaN substrate 110 and an extraction electrode 206 for etching is fixed to the support 204. The etching lead electrode 206 is the same as the metal electrode 60 as the etching lead electrode shown in FIG. That is, the etching lead electrode 206 has an opening provided at a position different from the opening 130a provided for recess formation with respect to the photoelectrochemical etching mask 130 in the structure 112 to be etched (see FIG. (Not shown) so as to be electrically connected to the GaN 106. The lead electrode 206 is connected to one end of a conducting wire 212, and the cathode 208 in the etchant is connected to the other end of the conducting wire 212 with an ammeter 210 interposed therebetween. For the cathode 208, a material having a high ionization tendency such as platinum, gold, silver, and carbon is used.

  Photoelectrochemical etching is performed by irradiating the etched structure 112 with light 220 having a short wavelength. In photoelectrochemical etching, it is necessary to make the wavelength of the light 220 to be irradiated shorter than the wavelength corresponding to the band gap energy of the semiconductor to be etched.

  Here, since the heterostructure of GaN / AlGaN is used as the structure to be etched 112, etching needs to be stopped at the interface of GaN / AlGaN (see FIG. 2D). The band cap energy of GaN is 3.4 eV, and the wavelength corresponding to this is 365 nm. The wavelength corresponding to the band gap energy of AlGaN is approximately 300 to 350 nm although it varies depending on the composition. Therefore, light having a wavelength shorter than 365 nm and longer than 300 to 350 nm is irradiated. As the light source for the short wavelength light, an ultra high pressure mercury lamp provided with a filter or a He—Cd laser having a wavelength of 325 nm is preferable.

  The structure to be etched 112 is irradiated with light having a wavelength selected as described above. As a result, electrons in the valence band of GaN are excited by the conductor, and the electrons are carried to the cathode. Since the cathode has a high ionization tendency, it receives electrons, ionizes, and dissolves into the solution. In addition, GaN that has lost electrons is decomposed by the following chemical formula.

2GaN + 6h ⁺ → 2Ga ³⁺ + N ₂
Here, h ⁺ means a hole due to loss of electrons. As a result, the GaN layer 106 is etched to form a recess 106a, and a structure 114 as shown in FIG. 2D is obtained. A portion of the AlGaN layer 104 is exposed in the recess 106a. The etching depth is controlled by monitoring the etching current.

A large amount of oxide such as Ga ₂ O ₃ is deposited on the surface subjected to photoelectrochemical etching. In order to remove the oxide, treatment with hot ammonia water or hydrochloric acid is performed.

  After this recess etching, a photoresist layer is applied and formed on the entire upper surface of the structure 114, and then patterned to have an opening 150a in the gate formation region of the photoresist layer, thereby obtaining a photoresist pattern 150 (see FIG. FIG. 3 (A)).

  Thereafter, a gate metal 160 is deposited on the photoresist pattern 150 on the upper surface. By the deposition of the gate metal 160, a gate metal portion 160a on the exposed surface of the AlGaN 104 exposed in the opening 150a and a gate metal portion 160b on the photoresist pattern 150 are formed (FIG. 3B). .

  Next, when the photoresist pattern 150 is lifted off, the gate metal portion 160b is partially removed together with the photoresist pattern 150 except for the gate metal portion 160a deposited in the opening 150a of the photoresist pattern 150, and the gate metal portion 160a. Remains as the gate electrode 162, and a GaN-HEMT structure is obtained as a semiconductor device (FIG. 3C).

(Effects of Group III Nitride Semiconductor Device Manufacturing Method)
After the silicon nitride film used as a mask for photoelectrochemical etching is etched, it can be used as a passivation film or an interlayer insulating film of a semiconductor device. Therefore, it is possible to omit a step of removing a mask after etching or a step of forming a passivation film or the like during the manufacturing process of a semiconductor device. Conventionally, since a dry etching method has been used as an etching method, it has been damaged by plasma ions, but the influence is eliminated.

It is process drawing for demonstrating embodiment of the formation method of the mask for photoelectrochemical etching. It is process drawing for demonstrating embodiment of the manufacturing method of recess gate GaN-HEMT using photoelectrochemical etching. It is process drawing for demonstrating embodiment of the manufacturing method of recess gate GaN-HEMT using photoelectrochemical etching. It is a figure for demonstrating the outline of an example of a photoelectrochemical etching apparatus.

Explanation of symbols

10, 110 GaN substrate 22, 24 Ohmic electrode 30 Preliminary mask layer 40, 150 Photoresist pattern 50, 130 Photoelectrochemical etching mask 60 Metal electrode 100 Si substrate 102, 106 GaN
104 AlGaN
106a recess 112 structure to be etched 114 structure 122 source electrode 124 drain electrode 160 gate metal 162 gate electrode 200 photoelectrochemical etching vessel 202 etchant 204 support 206 etching lead electrode 208 cathode 210 ammeter 212 lead 220 light of short wavelength

Claims (3)

In a mask used for photoelectrochemical etching of a group III nitride semiconductor,
A mask for photoelectrochemical etching comprising one or more mask materials selected from a mask material group consisting of silicon nitride, aluminum nitride, silicon oxide, aluminum oxide, silicon oxynitride and aluminum oxynitride . One or more mask materials selected from the mask material group consisting of silicon nitride, aluminum nitride, silicon oxide, aluminum oxide, silicon oxynitride, and aluminum oxynitride are formed on the entire upper surface of the group III nitride semiconductor substrate. A first step of forming a preliminary mask layer,
A second step of forming a photoresist pattern on the preliminary mask layer, and then patterning an opening in the photoresist layer to form a photoresist pattern;
A third step of forming an opening by etching away a region portion of the preliminary mask layer exposed in the opening of the photoresist pattern;
A method for forming a mask for photoelectrochemical etching, comprising: a fourth step of removing the photoresist pattern. A first step of forming a source electrode and a drain electrode on the surface of the group III nitride semiconductor substrate;
The entire upper surface of the group III nitride semiconductor substrate on which the source electrode and the drain electrode are formed is selected from a mask material group consisting of silicon nitride, aluminum nitride, silicon oxide, aluminum oxide, silicon oxynitride, and aluminum oxynitride. A second step of forming a preliminary mask layer made of one or more kinds of mask materials;
A third step of forming a photoresist pattern on the preliminary mask layer, and then patterning an opening in the photoresist layer to form a photoresist pattern;
A fourth step of forming an opening by etching away a region portion of the preliminary mask layer exposed in the opening of the photoresist pattern;
Removing the photoresist pattern to form a photoelectrochemical etching mask; and
A sixth step of performing photoelectrochemical etching on the group III nitride semiconductor substrate using the photoelectrochemical etching mask;
And a seventh step of forming a gate electrode in the portion etched by the photoelectrochemical etching.

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