TWI725010B - Etching solution, etching method and manufacturing method of semiconductor substrate product - Google Patents
Etching solution, etching method and manufacturing method of semiconductor substrate product Download PDFInfo
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Abstract
本發明提供一種可去除基板上的鈦的蝕刻液，使用其的蝕刻方法及半導體基板製品的製造方法。進而，本發明提供一種視需要可抑制基板上的含有矽或鍺的層、尤其是其矽化物層的損傷，並選擇性地去除含有鈦的層的蝕刻液，使用其的蝕刻方法及半導體基板製品的製造方法。The invention provides an etching solution capable of removing titanium on a substrate, an etching method using the etching solution, and a manufacturing method of semiconductor substrate products. Furthermore, the present invention provides an etching solution that can suppress damage to the silicon or germanium-containing layer on the substrate, especially the silicide layer, and selectively remove the titanium-containing layer as necessary, and an etching method and a semiconductor substrate using the same. The manufacturing method of the product.
Description
本發明是有關於一種蝕刻液、蝕刻方法及半導體基板製品的製造方法。 The invention relates to an etching solution, an etching method and a manufacturing method of semiconductor substrate products.
積體電路的製造包含多階段的各種加工步驟。於其製造過程中，反覆進行數次各種材料的堆積、微影及蝕刻等。其中，蝕刻成為重要的製程。必須選擇性地對特定的材料進行蝕刻，並使其他材料不腐蝕而殘存。有時要求以使包含類似金屬種類的該類層的一者、或包含腐蝕性更高的材料的層殘留的形態僅去除既定的層。近年來，半導體基板內的配線或積體電路的尺寸變得越來越小，並不腐蝕應殘留的構件而準確地進行蝕刻的重要性正提高。 The manufacture of integrated circuits includes various processing steps in multiple stages. During its manufacturing process, various materials are deposited, lithographically and etched repeatedly. Among them, etching has become an important process. It is necessary to selectively etch specific materials, and make other materials not corrode and remain. It is sometimes required to remove only a predetermined layer in a form in which one of such layers containing similar metal types or a layer containing a more corrosive material remains. In recent years, the size of wiring or integrated circuits in semiconductor substrates has become smaller and smaller, and the importance of accurately etching without corroding the remaining components is increasing.
若舉場效電晶體為例來看，伴隨其急速的微細化，而強烈要求形成於源極區域及/或汲極區域的上表面的矽化物層的薄膜化、或新型材料的開發。於形成該矽化物層的自對準矽化製程(Salicide：Self-Aligned Silicide)中，對形成於半導體基板上的包含矽等的源極區域及汲極區域的一部分、與附加於其上表面的金屬層進行退火。藉此，可於源極電極及/或汲極電極等的上側形成低電阻的矽化物層。 Taking a field-effect transistor as an example, with its rapid miniaturization, there is a strong demand for the thinning of the silicide layer formed on the upper surface of the source region and/or the drain region, or the development of new materials. In the self-aligned silicide (Salicide: Self-Aligned Silicide) process for forming the silicide layer, a part of the source region and the drain region including silicon, etc., formed on the semiconductor substrate, and the The metal layer is annealed. Thereby, a low-resistance silicide layer can be formed on the upper side of the source electrode and/or the drain electrode.
於自對準矽化步驟後，藉由蝕刻來去除殘留於其中的金屬層。該蝕刻通常藉由濕式蝕刻來進行，作為其藥液，應用鹽酸與硝酸的混合液(王水)。專利文獻1揭示有使用除硝酸及鹽酸以外，添加有甲苯磺酸的藥液作為去除Ni及Pt者的例子。
After the self-aligned silicidation step, the remaining metal layer is removed by etching. This etching is usually performed by wet etching, and a mixed solution of hydrochloric acid and nitric acid (aqua regia) is used as the chemical solution.
[現有技術文獻] [Prior Art Literature]
[專利文獻] [Patent Literature]
[專利文獻1]：國際公開第2012/125401號手冊 [Patent Document 1]: International Publication No. 2012/125401 Handbook
本發明的課題在於提供一種可去除基板上的鈦的蝕刻液，使用其的蝕刻方法及半導體基板製品的製造方法。進而，本發明的課題在於提供一種視需要可抑制基板上的含有矽或鍺的層、尤其是其矽化物層的損傷，並選擇性地去除含有鈦的層的蝕刻液，使用其的蝕刻方法及半導體基板製品的製造方法。 The subject of the present invention is to provide an etching solution capable of removing titanium on a substrate, an etching method using the etching solution, and a manufacturing method of a semiconductor substrate product. Furthermore, the subject of the present invention is to provide an etching method that can suppress the damage of the silicon or germanium-containing layer on the substrate, especially the silicide layer, and selectively remove the titanium-containing layer as necessary, and an etching method using the same. And the manufacturing method of semiconductor substrate products.
所述課題可藉由以下的手段來解決。 The problem can be solved by the following means.
[1]一種蝕刻液，其為半導體製程用的蝕刻液，且含有氟離子與取代對苯二酚化合物。 [1] An etching solution, which is an etching solution for semiconductor manufacturing and contains fluorine ions and substituted hydroquinone compounds.
[2]如[1]所述的蝕刻液，其含有有機溶媒。 [2] The etching solution according to [1], which contains an organic solvent.
[3]如[1]或[2]所述的蝕刻液，其含有水。 [3] The etching solution according to [1] or [2], which contains water.
[4]如[1]至[3]中任一項所述的蝕刻液，其中所述氟離子的濃度為0.1質量%以上、20質量%以下。 [4] The etching solution according to any one of [1] to [3], wherein the concentration of the fluorine ion is 0.1% by mass or more and 20% by mass or less.
[5]如[1]至[4]中任一項所述的蝕刻液，其中所述取代對苯二酚化合物的濃度為0.1質量%以上、10質量%以下。 [5] The etching solution according to any one of [1] to [4], wherein the concentration of the substituted hydroquinone compound is 0.1% by mass or more and 10% by mass or less.
[6]如[2]所述的蝕刻液，其中所述有機溶媒的濃度為50質量%以上、98質量%以下。 [6] The etching solution according to [2], wherein the concentration of the organic solvent is 50% by mass or more and 98% by mass or less.
[7]如[3]所述的蝕刻液，其中所述水的濃度為0.1質量%以上、50質量%以下。 [7] The etching solution according to [3], wherein the concentration of the water is 0.1% by mass or more and 50% by mass or less.
[8]如[1]至[7]中任一項所述的蝕刻液，其中所述取代對苯二酚化合物由下述式(H1)所表示。 [8] The etching solution according to any one of [1] to [7], wherein the substituted hydroquinone compound is represented by the following formula (H1).
RH1表示取代基。m1表示1~4的整數。 R H1 represents a substituent. m1 represents an integer from 1 to 4.
[9]如[8]所述的蝕刻液，其中RH1為烴基。 [9] The etching solution according to [8], wherein R H1 is a hydrocarbon group.
[10]如[9]所述的蝕刻液，其中RH1為烷基。 [10] The etching solution according to [9], wherein R H1 is an alkyl group.
[11]如[1]至[10]中任一項所述的蝕刻液，其中所述取代對苯二酚化合物的ClogP值為1以上、10以下。 [11] The etching solution according to any one of [1] to [10], wherein the ClogP value of the substituted hydroquinone compound is 1 or more and 10 or less.
[12]如[1]至[11]中任一項所述的蝕刻液，其中所述取代對苯二酚化合物為2,5-二-第三丁基對苯二酚、2-第三丁基對苯二酚、2,5- 二甲基對苯二酚、或2-甲基對苯二酚。 [12] The etching solution according to any one of [1] to [11], wherein the substituted hydroquinone compound is 2,5-di-tertiary butyl hydroquinone, 2-tertiary hydroquinone Butylhydroquinone, 2,5- Dimethylhydroquinone, or 2-methylhydroquinone.
[13]如[1]至[12]中任一項所述的蝕刻液，其中所述取代對苯二酚化合物相對於矽基板的腐蝕電位為-0.25V以上、0.5V以下。 [13] The etching solution according to any one of [1] to [12], wherein the corrosion potential of the substituted hydroquinone compound with respect to the silicon substrate is -0.25 V or more and 0.5 V or less.
[14]如[2]所述的蝕刻液，其中所述有機溶媒包含醇化合物或醚化合物。 [14] The etching solution according to [2], wherein the organic solvent contains an alcohol compound or an ether compound.
[15]如[2]所述的蝕刻液，其中所述有機溶媒包含由下述式(O-1)所表示的化合物。 [15] The etching solution according to [2], wherein the organic solvent contains a compound represented by the following formula (O-1).
RO1-(-O-RO2-)n-ORO3…(O-1) R O1 -(-OR O2 -) n -OR O3 …(O-1)
RO1及RO3分別獨立地為氫原子或碳數1~12的烷基、碳數6~14的芳基、或者碳數7~15的芳烷基。 R O1 and R O3 are each independently a hydrogen atom or an alkyl group having 1 to 12 carbons, an aryl group having 6 to 14 carbons, or an aralkyl group having 7 to 15 carbons.
RO2為直鏈狀或分支狀的碳數1以上、12以下的伸烷基鏈。當存在多個RO2時，各RO2可不同。 R O2 is a linear or branched alkylene chain having 1 to 12 carbon atoms. When there are multiple RO2 , each RO2 may be different.
n為0以上、12以下的整數。其中，當n為0時，RO1及RO3不同時為氫原子。 n is an integer of 0 or more and 12 or less. Wherein, when n is 0, R O1 and R O3 are not hydrogen atoms at the same time.
[16]如[1]至[15]中任一項所述的蝕刻液，其中所述半導體製程用的基板具有含有鈦的層與含有矽化鈦的層。 [16] The etching solution according to any one of [1] to [15], wherein the substrate for the semiconductor process has a layer containing titanium and a layer containing titanium silicide.
[17]如[16]所述的蝕刻液，其中所述含有鈦的層的蝕刻速度除以所述含有矽化鈦的層的蝕刻速度所得的值為4以上、15以下。 [17] The etching solution according to [16], wherein a value obtained by dividing the etching rate of the titanium-containing layer by the etching rate of the titanium silicide-containing layer is 4 or more and 15 or less.
[18]一種蝕刻方法，其應用如[1]至[17]中任一項所述的蝕刻液來進行含有鈦的層的蝕刻。 [18] An etching method that applies the etching solution described in any one of [1] to [17] to perform etching of a layer containing titanium.
[19]如[18]所述的蝕刻方法，其中一邊抑制矽化鈦的蝕刻，一邊進行所述含有鈦的層的蝕刻。 [19] The etching method according to [18], wherein etching of the titanium-containing layer is performed while suppressing the etching of titanium silicide.
[20]一種半導體基板製品的製造方法，其經由如[18]或[19]所述的蝕刻方法來製造半導體基板製品。 [20] A method of manufacturing a semiconductor substrate product, which manufactures a semiconductor substrate product through the etching method as described in [18] or [19].
根據本發明的蝕刻液、使用其的蝕刻方法及半導體基板製品的製造方法，可去除基板上的鈦。進而，視需要可抑制基板上的含有矽或鍺的層、尤其是其矽化物層的損傷，並選擇性地去除含有鈦的層。 According to the etching solution of the present invention, the etching method using the same, and the manufacturing method of a semiconductor substrate product, titanium on the substrate can be removed. Furthermore, if necessary, it is possible to suppress damage to the silicon or germanium-containing layer on the substrate, especially the silicide layer, and to selectively remove the titanium-containing layer.
本發明的以上所述及其他特徵以及優點可參照適宜隨附的圖式並根據下述記載而更明瞭。 The above and other features and advantages of the present invention can be made clearer with reference to the accompanying drawings as appropriate and based on the following description.
1:金屬層(第二層) 1: Metal layer (second layer)
2:含有矽(silicon)或鍺的層(第一層) 2: A layer containing silicon or germanium (the first layer)
3:矽化物層(第三層) 3: Silicide layer (third layer)
11:處理容器(處理槽) 11: Processing container (processing tank)
12:旋轉台 12: Rotating table
13:噴出口 13: spout
14:分岔點 14: bifurcation point
21:矽基板 21: Silicon substrate
22:閘極絕緣膜 22: Gate insulating film
23:閘極電極 23: Gate electrode
25:側壁 25: side wall
26:源極電極 26: Source electrode
26A:TiSi(Ge)源極電極部 26A: TiSi (Ge) source electrode
26B:經退火的矽化物源極電極 26B: Annealed silicide source electrode
27:汲極電極 27: Drain electrode
27A:TiSi(Ge)汲極電極部 27A: TiSi (Ge) drain electrode
27B:經退火的矽化物汲極電極 27B: Annealed silicide drain electrode
28:Ti膜 28: Ti film
A:藥液供給口 A: Liquid medicine supply port
fc、fd:流路 fc, fd: flow path
M:旋轉驅動部 M: Rotary drive unit
r:方向 r: direction
S:半導體基板 S: Semiconductor substrate
t:移動軌跡線 t: moving trajectory
圖1(a)、圖1(b)、圖1(c)是示意性地表示本發明的一實施形態中的半導體基板的製作步驟例的剖面圖。 Figs. 1(a), 1(b), and 1(c) are cross-sectional views schematically showing examples of manufacturing steps of a semiconductor substrate in an embodiment of the present invention.
圖2(A)、圖2(B)、圖2(C)、圖2(D)及圖2(E)是表示本發明的一實施形態中的金屬氧化物半導體(Metal Oxide Semiconductor，MOS)電晶體的製造例的步驟圖。 Figures 2(A), 2(B), 2(C), 2(D) and 2(E) show a metal oxide semiconductor (MOS) in an embodiment of the present invention Step diagram of the manufacturing example of the transistor.
圖3是表示本發明的較佳的實施形態的濕式蝕刻裝置的一部分的裝置構成圖。 Fig. 3 is an apparatus configuration diagram showing a part of a wet etching apparatus according to a preferred embodiment of the present invention.
圖4是示意性地表示本發明的一實施形態中的相對於半導體基板的噴嘴的移動軌跡線的平面圖。 4 is a plan view schematically showing the movement trajectory of the nozzle with respect to the semiconductor substrate in one embodiment of the present invention.
首先，根據圖1(a)、圖1(b)、圖1(c)、圖2(A)、圖2(B)、圖2(C)、圖2(D)及圖2(E)對與本發明的蝕刻液的應用相關的蝕刻步驟的較佳的實施形態進行說明。 First, according to Figure 1 (a), Figure 1 (b), Figure 1 (c), Figure 2 (A), Figure 2 (B), Figure 2 (C), Figure 2 (D) and Figure 2 (E) A preferred embodiment of the etching step related to the application of the etching solution of the present invention will be described.
[蝕刻步驟] [Etching step]
圖1(a)、圖1(b)、圖1(c)是表示蝕刻前後的半導體基板的圖。於本實施形態的製造例中，在含有矽(silicon)或鍺的層(第一層)2的上表面配置有金屬層(第二層)1。作為含有矽或鍺的層(第一層)，應用構成源極電極、汲極電極的Si磊晶層。第一層可包含Si，亦可為SiGe磊晶層或Ge磊晶層。 Fig. 1(a), Fig. 1(b), and Fig. 1(c) are diagrams showing the semiconductor substrate before and after etching. In the manufacturing example of this embodiment, a metal layer (second layer) 1 is arranged on the upper surface of a layer (first layer) 2 containing silicon or germanium. As the layer (first layer) containing silicon or germanium, a Si epitaxial layer constituting a source electrode and a drain electrode is used. The first layer may include Si, or may be a SiGe epitaxial layer or a Ge epitaxial layer.
作為金屬層(第二層)1的構成材料，可設為鈦(Ti)。金屬層的形成通常可使用應用於此種金屬膜的形成的方法，具體而言，可列舉利用化學氣相沈積(Chemical Vapor Deposition，CVD)的成膜。此時的金屬層的厚度並無特別限定，可列舉5nm以上、50nm以下的膜的例子。於本發明中，當金屬層為Ti層時，蝕刻液的去除性能得以充分地發揮，故較佳。 As a constituent material of the metal layer (second layer) 1, titanium (Ti) can be used. The formation of the metal layer can generally use a method applied to the formation of such a metal film, and specifically, film formation by chemical vapor deposition (CVD) can be mentioned. The thickness of the metal layer at this time is not particularly limited, and examples of films having a thickness of 5 nm or more and 50 nm or less can be cited. In the present invention, when the metal layer is a Ti layer, the removal performance of the etching solution can be fully exerted, which is preferable.
除所述列舉的金屬原子以外，金屬層亦可含有其他元素。例如，亦可存在不可避免地混入的氧或氮。不可避免的雜質的量較佳為抑制成例如1ppt~10ppm(質量基準)左右。 In addition to the metal atoms listed above, the metal layer may also contain other elements. For example, there may be oxygen or nitrogen inevitably mixed in. The amount of inevitable impurities is preferably suppressed to, for example, about 1 ppt to 10 ppm (based on mass).
另外，於半導體基板中，除所述材料以外，有時存在不期望被蝕刻的材料。於本發明的較佳的實施形態的蝕刻液中，可進而抑制此種材料的腐蝕等而較佳。 In addition, in the semiconductor substrate, in addition to the above-mentioned materials, there may be materials that are not desired to be etched. In the etching solution of the preferred embodiment of the present invention, corrosion of such materials can be further suppressed, which is preferable.
於圖1的步驟(a)中，在含有矽或鍺的層2的上側形成金屬層1後，進行退火(燒結)，而於其界面上形成金屬-Si反應膜(第三層：矽化物層)3(圖1的步驟(b))。退火只要利用通常應用於此種元件的製造的條件即可，例如可列舉於200℃~1000℃下進行處理。此時的矽化物層3的厚度並無特別限定，可列舉成為50nm以下的層的例子，進而可列舉成為10nm以下的層的例子。並不特別存在下限值，但較實際的是1nm以上。該矽化物層可用作低電阻膜，作為將位於其下部的源極電極及/或汲極電極與配置於其上部的配線電性連接的導電部而發揮功能。因此，若於矽化物層中產生缺損或腐蝕，則該導通受到阻礙，有時會帶來元件誤操作等品質下降。尤其，最近基板內部的積體電路結構正不斷微細化，即便是微小的損傷，亦可能對元件的性能造成大的影響。因此，理想的是儘可能地防止此種缺損及腐蝕。
In step (a) of FIG. 1, after forming the
於本說明書中，廣義上而言，矽化物層是包含於第一層的含有矽或鍺的層中的概念。因此，當相對於第一層而選擇性地去除第二層時，表示不僅是相對於未矽化的含有矽或鍺的層而優先去除第二層(金屬層)的形態，而且包含相對於矽化物層而優先去除第二層(金屬層)的形態。狹義上，當將第一層的含有矽或鍺的層(矽化物層除外)與第三層的矽化物層區別稱呼時，分別稱為第一層及第三層。再者，所述矽的層可為單晶矽、多晶矽或非晶矽的任一者。另外，當僅稱為矽化物層時，表示包含對各金屬進行退火所形成的複合金屬層。因此，當稱為矽化鈦時，表 示不僅包括鈦與矽的矽化物，而且包括包含鈦與矽及鍺的矽化物、或包含鈦與鍺的矽化物。於本發明中，就其效果變得顯著的觀點而言，較佳為應用於包含鈦及矽的矽化物層(TiSi)、或包含鈦、矽、及鍺的矽化物層(TiSiGe)的保護，更佳為應用於包含鈦及矽的矽化物層(TiSi)的保護。 In this specification, broadly speaking, the silicide layer is a concept included in the silicon or germanium-containing layer of the first layer. Therefore, when the second layer is selectively removed relative to the first layer, it means not only that the second layer (metal layer) is preferentially removed relative to the unsilicided layer containing silicon or germanium, but also includes The morphology of the second layer (metal layer) is preferentially removed. In a narrow sense, when the first layer containing silicon or germanium (except the silicide layer) and the third layer of silicide layer are called differently, they are called the first layer and the third layer, respectively. Furthermore, the silicon layer can be any of single crystal silicon, polycrystalline silicon, or amorphous silicon. In addition, when it is simply called a silicide layer, it means that it includes a composite metal layer formed by annealing each metal. Therefore, when it is called titanium silicide, the table The display includes not only silicides of titanium and silicon, but also silicides of titanium, silicon and germanium, or silicides of titanium and germanium. In the present invention, from the viewpoint that its effect becomes remarkable, it is preferably applied to the protection of a silicide layer (TiSi) containing titanium and silicon, or a silicide layer containing titanium, silicon, and germanium (TiSiGe) , More preferably used in the protection of silicide layers (TiSi) containing titanium and silicon.
繼而，進行殘存的金屬層1的蝕刻(圖1的步驟(b)、>步驟(c))。於本實施形態中，此時應用蝕刻液，自金屬層1的上側賦予蝕刻液來進行接觸，藉此去除金屬層1。蝕刻液的賦予的形態將後述。
Then, the remaining
含有矽或鍺的層2可包含Si磊晶層或SiGe磊晶層，並藉由化學氣相沈積(CVD)法而於具有特定的結晶性的矽基板上結晶成長來形成。或者，亦可藉由分子束磊晶(Molecular Beam Epitaxy：MBE)法等，製成以所期望的結晶性而形成的磊晶層。
The
為了將含有矽或鍺的層設為P型層，較佳為摻雜濃度為1×1014cm-3~1×1021cm-3左右的硼(B)。為了設為N型層，較佳為以1×1014cm-3~1×1021cm-3的濃度摻雜磷(P)或砷(As)。 In order to make the layer containing silicon or germanium a P-type layer, the doping concentration of boron (B) is preferably about 1×10 14 cm -3 to 1×10 21 cm -3. In order to be an N-type layer, it is preferable to dope phosphorus (P) or arsenic (As) at a concentration of 1×10 14 cm -3 to 1×10 21 cm -3.
當第一層為SiGe磊晶層時，其Ge濃度較佳為20質量%以上，更佳為40質量%以上。作為上限，較佳為100質量%以下，更佳為90質量%以下。再者，當鍺為100質量%時，藉由其退火而伴隨第二層的合金所形成的層包含鍺與第二層的特定金屬元素，並不含矽，但如上所述，於本說明書中為便於說明，包含其在內而稱為鍺「矽化物」層。 When the first layer is a SiGe epitaxial layer, its Ge concentration is preferably 20% by mass or more, more preferably 40% by mass or more. As the upper limit, it is preferably 100% by mass or less, and more preferably 90% by mass or less. Furthermore, when germanium is 100% by mass, the layer formed by the annealing of the alloy of the second layer contains germanium and the specific metal element of the second layer, and does not contain silicon. However, as described above, in this specification For convenience of description, it is included as a germanium "silicide" layer.
於本說明書中，將鍺的濃度設為藉由以下的測定方法所測定的值。利用蝕刻化學分析電子能譜儀(Electron Spectroscopy for Chemical Analysis，ESCA)(日本真空(ULVAC-PHI)製造 商品名：克安太拉(Quantera))，對含有鍺(Ge)的層的基板的自0nm至30nm為止的深度方向進行分析，並將3nm~15nm的分析結果中的Ge濃度的平均值設為Ge濃度(質量%)。 In this specification, the concentration of germanium is the value measured by the following measurement method. Using Electron Spectroscopy for Chemical Analysis (ESCA) (product name: Quantera) manufactured by ULVAC-PHI, the self-contained germanium (Ge) layer of the substrate The analysis is performed in the depth direction from 0 nm to 30 nm, and the average value of the Ge concentration in the analysis results of 3 nm to 15 nm is defined as the Ge concentration (mass %).
經過自對準矽化步驟，在所述含有矽或鍺的層(第一層)與金屬層(第二層)之間，形成矽化物層作為含有矽(Si)或鍺(Ge)及第二層的成分(所述特定金屬種)的層。該矽化物層廣義上包含於所述第一層中，但當狹義上與所述第一層區別稱呼時稱為「第三層」。其組成若以式SixGeyMz(M：金屬元素)而言，則較佳為設為x+y+z=1、且0.2≦x+y≦0.8，更佳為0.3≦x+y≦0.7。關於z，較佳為0.2≦z≦0.8，更佳為0.3≦z≦0.7。x與y的比率的較佳的範圍較佳為y=0(不含Ge)，當含有Ge時，如所述規定般。其中，於第三層中亦可含有其他元素。此方面與所述金屬層(第二層)中所述者相同。 After a self-aligned silicidation step, a silicide layer is formed between the silicon or germanium-containing layer (first layer) and the metal layer (second layer) as a silicide layer containing silicon (Si) or germanium (Ge) and a second layer. The layer of the composition (the specific metal species) of the layer. The silicide layer is included in the first layer in a broad sense, but is called the "third layer" when it is called differently from the first layer in a narrow sense. If its composition is based on the formula Si x Ge y M z (M: metal element), it is preferably set to x+y+z=1, 0.2≦x+y≦0.8, and more preferably 0.3≦x+ y≦0.7. Regarding z, 0.2≦z≦0.8 is preferable, and 0.3≦z≦0.7 is more preferable. The preferable range of the ratio of x to y is preferably y=0 (excluding Ge), and when Ge is contained, it is as described above. Among them, other elements may also be contained in the third layer. This aspect is the same as that described in the metal layer (second layer).
(MOS電晶體的加工) (Processing of MOS transistor)
圖2(A)、圖2(B)、圖2(C)、圖2(D)及圖2(E)是表示MOS電晶體的製造例的步驟圖。圖2(A)為MOS電晶體結構的形成步驟，圖2(B)為金屬膜的濺鍍步驟，圖2(C)為第1次的退火步驟，圖2(D)為金屬膜的選擇去除步驟，圖2(E)為第2次的退火步驟。 2(A), FIG. 2(B), FIG. 2(C), FIG. 2(D), and FIG. 2(E) are process diagrams showing examples of manufacturing MOS transistors. Fig. 2(A) is the formation step of the MOS transistor structure, Fig. 2(B) is the sputtering step of the metal film, Fig. 2(C) is the first annealing step, and Fig. 2(D) is the selection of the metal film The removal step, Fig. 2(E) is the second annealing step.
如圖2(A)所示，經由形成於矽基板21的表面的閘極絕緣膜22而形成閘極電極23。於矽基板21的閘極電極23的兩側可另外形成外延(extension)區域。於閘極電極23的上側可形成防止與Ti層的接觸的保護層(未圖示)。進而，形成包含氧化矽膜或氮化矽膜的側壁25，藉由離子注入而形成源極區域26及汲極區域27。
As shown in FIG. 2(A), the
繼而，如圖2(B)、圖2(C)所示，形成Ti膜28，實施急速退火處理。藉此，使Ti膜28中的元素擴散至矽基板中而使其矽化(於本說明書中，亦包含鍺為100質量%時，為便於說明，將利用退火的合金化稱為矽化)。其結果，源極電極26及汲極電極27的上部被矽化，形成TiSi(Ge)源極電極部26A及TiSi(Ge)汲極電極部27A。此時，視需要如圖2(E)所示般進行第2次的退火，藉此使電極構件變化成所期望的狀態(經退火的矽化物源極電極26B、經退火的矽化物汲極電極27B)。所述第1次與第2次的退火溫度並無特別限定，例如可於400℃~1100℃下進行。
Then, as shown in FIG. 2(B) and FIG. 2(C), a
無助於矽化而殘留的Ti膜28可藉由使用本發明的蝕刻液來去除(圖2(C)、圖2(D))。此時，將所圖示者大幅度地模式化而進行表示，堆積於經矽化的層(26A、27A)的上部而殘留的Ti膜可有可無。半導體基板或其製品的結構亦簡化地進行圖示，視需要只要作為具有必要的構件者進行解釋即可。
The remaining
若列舉構成材料的較佳例，則可例示如下所述的形態。 If a preferable example of the constituent material is given, the following forms can be exemplified.
21 矽基板：Si、SiGe、Ge 21 Silicon substrate: Si, SiGe, Ge
22 閘極絕緣膜：HfO2(高介電常數(High-k)) 22 Gate insulating film: HfO 2 (High-k)
23 閘極電極：Al、W 23 Gate electrode: Al, W
25 側壁：SiOCN、SiN、SiO2(低介電常數(low-k)) 25 Sidewall: SiOCN, SiN, SiO 2 (low-k)
26 源極電極：Si、SiGe、Ge 26 Source electrode: Si, SiGe, Ge
27 汲極電極：Si、SiGe、Ge 27 Drain electrode: Si, SiGe, Ge
28 金屬層：Ti 28 Metal layer: Ti
未圖示 蓋：TiN Not shown Cover: TiN
以上敍述了應用本發明的蝕刻液的半導體基板的例子，但並不限於該具體例，亦可應用於其他半導體基板。例如可列舉：於源極區域及/或汲極區域上包含具有矽化物圖案的高介電膜/金屬閘極鰭式場效電晶體(Fin Field Effect Transistor，FinFET)的半導體基板。 The example of the semiconductor substrate to which the etching liquid of this invention is applied is described above, but it is not limited to this specific example, It can apply to other semiconductor substrates. For example, a semiconductor substrate including a high-dielectric film with a silicide pattern/metal gate fin field effect transistor (Fin Field Effect Transistor, FinFET) on the source region and/or the drain region can be cited.
此處，若談到殘留矽化物層(第三層)或矽等的層(第一層)，僅去除其上層的金屬層(第二層)的困難性，則可列舉矽化物層包含應去除的金屬而構成這一方面。即，若為了提高金屬層的去除性而採用其溶解性高的溶液成分，則包含該金屬的矽化物層亦會容易溶解。另外，若應用形成矽化物的金屬(Ti、Pt及Ni等)的溶解性高的成分，則通常變成對於矽(Si)及鍺(Ge)亦顯示出溶解性的方向。因此，提高金屬層的溶解性，另一方面，抑制其矽化物層等的損傷變成相反的方向。根據本發明的較佳的實施形態，可實現此種難以並存的特性，保護作為半導體基板製品所欲殘留的矽化物層等，並有效地去除位於其上側等的金屬層。 Here, when it comes to the difficulty of removing the remaining silicide layer (third layer) or silicon layer (first layer), only the metal layer (second layer) above it, the silicide layer contains applications The removed metal constitutes this aspect. That is, if a solution component with high solubility is used in order to improve the removability of the metal layer, the silicide layer containing the metal will also be easily dissolved. In addition, if a component with a high solubility of the metal (Ti, Pt, Ni, etc.) forming silicide is applied, it will usually become a direction that also shows solubility for silicon (Si) and germanium (Ge). Therefore, the solubility of the metal layer is improved, and on the other hand, the damage of the silicide layer or the like is suppressed from turning in the opposite direction. According to the preferred embodiment of the present invention, it is possible to realize such characteristics that are difficult to coexist, protect the silicide layer etc. remaining as a semiconductor substrate product, and effectively remove the metal layer located on the upper side thereof.
[蝕刻液] [Etching Solution]
繼而，對本發明的蝕刻液的較佳的實施形態進行說明。本實施形態的蝕刻液含有氟離子與取代對苯二酚化合物。此處，所謂取代對苯二酚化合物，是去除對苯二酚化合物中未經取代者的含義。於蝕刻液中，進而視需要亦可含有有機溶媒或水。其中，較佳為所述蝕刻液實質上僅包含氟離子、其抗衡離子、取代對苯二酚化合物、水及有機溶媒。此處，「實質上」是指於起到本發明的效果的範圍內，可包含不可避免的雜質或微量添加成分。以下，對各成分進行說明。 Next, a preferable embodiment of the etching solution of the present invention will be described. The etching solution of this embodiment contains fluorine ions and a substituted hydroquinone compound. Here, the term "substituted hydroquinone compound" refers to the removal of unsubstituted hydroquinone compounds. The etching solution may further contain an organic solvent or water as necessary. Among them, it is preferable that the etching solution substantially contains only fluoride ions, counter ions, substituted hydroquinone compounds, water, and organic solvents. Here, "substantially" means that unavoidable impurities or trace addition components may be included in the range where the effect of the present invention is exerted. Hereinafter, each component will be described.
(氟離子) (Fluoride ion)
於本發明的蝕刻液中含有氟離子。可理解為於蝕刻液中，氟離子變成第二層的金屬(Ti等)的配位體(錯合劑)並發揮促進溶解的作用。 The etching solution of the present invention contains fluorine ions. It can be understood that in the etching solution, the fluorine ion becomes a ligand (complexing agent) of the second layer of metal (Ti, etc.) and plays a role of promoting dissolution.
於蝕刻液中，氟離子的濃度較佳為0.1質量%以上，更佳為0.5質量%以上，特佳為含有1質量%以上。作為上限，較佳為20質量%以下，更佳為10質量%以下，進而更佳為5質量%以下，特佳為2質量%以下。藉由以所述濃度應用氟離子，可實現良好的金屬層的蝕刻，並實現矽或鍺的層、或者其矽化物層的有效的保護，故較佳。 In the etching solution, the concentration of fluoride ions is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and particularly preferably 1% by mass or more. As the upper limit, it is preferably 20% by mass or less, more preferably 10% by mass or less, still more preferably 5% by mass or less, and particularly preferably 2% by mass or less. By applying fluorine ions at the above concentration, good etching of the metal layer can be achieved, and effective protection of the silicon or germanium layer or the silicide layer thereof can be achieved, which is preferable.
再者，於確認調配量時，可藉由對製造時的氟化合物(鹽)的量進行定量，而特定氟離子的量。含氟化合物可僅使用一種，亦可併用兩種以上來使用。作為氟離子的供給源，可列舉下述列 表中者。於本發明中，其中較佳為氫氟酸(HF)。 In addition, when confirming the compounding amount, the amount of the fluorine ion can be specified by quantifying the amount of the fluorine compound (salt) at the time of production. Only one type of fluorine-containing compound may be used, or two or more types may be used in combination. As a supply source of fluoride ions, the following can be cited Those in the table. In the present invention, among them, hydrofluoric acid (HF) is preferred.
(取代對苯二酚化合物) (Substituted hydroquinone compound)
於本發明的蝕刻液中，含有取代對苯二酚化合物(較佳為烷基取代對苯二酚)。所述取代對苯二酚化合物廣泛包含具有對苯二酚骨架的化合物，所述對苯二酚骨架具有取代基。於本發明的蝕刻液中，可理解為取代對苯二酚化合物能夠與所述氟離子協同作用來達成適當的金屬的去除性、及含有矽或鍺的層(較佳為其矽化物層)的保護性。若包含推斷來說，可理解為於含有氟離子的系中Ti與Si等的親水性的不同發揮作用(後者為疏水性)，於疏水性高的化合物中具有特定的對苯二酚骨架的化合物於其矽化物層等的吸附性(保護性)方面優異。其結果，可認為取代對苯二酚化合物相對於所述矽化物層等形成特有的吸附層，並顯示出氟 離子抑制過度損傷(溶解)的作用。另一方面，可理解為不阻礙對氟離子所期待的作用(金屬的溶解作用等)，且其結果同時發揮高的金屬層的去除性與對於矽化物層等的良好的保護性。 The etching solution of the present invention contains a substituted hydroquinone compound (preferably an alkyl substituted hydroquinone). The substituted hydroquinone compound broadly includes compounds having a hydroquinone skeleton, and the hydroquinone skeleton has a substituent. In the etching solution of the present invention, it can be understood that the substituted hydroquinone compound can synergize with the fluoride ion to achieve proper metal removal, and a layer containing silicon or germanium (preferably a silicide layer) Of protection. If including inference, it can be understood that the difference in hydrophilicity between Ti and Si in the system containing fluoride ions (the latter is hydrophobic) plays a role, and has a specific hydroquinone skeleton in compounds with high hydrophobicity. The compound is excellent in the adsorbability (protective property) of the silicide layer and the like. As a result, it can be considered that the substituted hydroquinone compound forms a peculiar adsorption layer with respect to the silicide layer and the like, and exhibits fluorine Ions inhibit excessive damage (dissolution). On the other hand, it can be understood that the expected effect on the fluoride ion (metal dissolution effect, etc.) is not hindered, and as a result, high metal layer removability and good protection against the silicide layer and the like are exhibited at the same time.
所述取代對苯二酚化合物較佳為由下述式(H1)所表示。 The substituted hydroquinone compound is preferably represented by the following formula (H1).
RH1表示取代基。作為取代基，較佳為烷基(碳數較佳為1~12，更佳為2~6，特佳為2~4)、烯基(碳數較佳為2~12，更佳為2~6)、芳基(碳數較佳為6~22，更佳為6~14，特佳為6~10)、芳烷基(碳數較佳為6~22，更佳為6~14，特佳為6~10)、含有羥基的基、含有羧基的基、含有硫醇基(硫基)的基、含有胺基的基(胺基的碳數較佳為0~6，更佳為0~3)。含有羥基的基、含有羧基的基、含有硫醇基的基、含有胺基的基的連結基較佳為無連結基的形態(單鍵)。當含有連結基時，該連結基較佳為伸烷基(碳數較佳為1~12，更佳為1~6，特佳為1~3)、伸烯基(碳數較佳為2~12，更佳為2~6)、O、CO、NRN、S、或與其組合相關的基。除氫原子以外，構成連結基的原子的數量較 佳為1~12，更佳為1~6，特佳為1~3。連結基的連結原子數較佳為10以下，更佳為8以下，特佳為3以下。下限為1以上。所述連結原子數是指位於將既定的結構部間連結的路徑上並參與連結的最少的原子數。例如，於-CH2-C(=O)-O-的情況下，構成連結基的原子的數量變成6，但連結原子數變成3。 R H1 represents a substituent. As the substituent, an alkyl group (the carbon number is preferably 1 to 12, more preferably 2 to 6, particularly preferably 2 to 4), and an alkenyl group (the carbon number is preferably 2 to 12, more preferably 2 ~6), aryl (the carbon number is preferably 6-22, more preferably 6-14, particularly preferably 6-10), aralkyl (the carbon number is preferably 6-22, more preferably 6-14 , Particularly preferably 6-10), hydroxyl-containing groups, carboxyl-containing groups, thiol (thio)-containing groups, amine-containing groups (the carbon number of the amine group is preferably 0-6, more preferably It is 0~3). The linking group of the hydroxyl group-containing group, the carboxyl group-containing group, the thiol group-containing group, and the amine group-containing group is preferably in the form of no linking group (single bond). When it contains a linking group, the linking group is preferably an alkylene group (the carbon number is preferably 1 to 12, more preferably 1 to 6, particularly preferably 1 to 3), and an alkenylene group (the carbon number is preferably 2 ~12, more preferably 2~6), O, CO, NR N , S, or a group related to a combination thereof. In addition to hydrogen atoms, the number of atoms constituting the linking group is preferably 1-12, more preferably 1-6, and particularly preferably 1-3. The number of linking atoms of the linking group is preferably 10 or less, more preferably 8 or less, and particularly preferably 3 or less. The lower limit is 1 or more. The number of connecting atoms refers to the minimum number of atoms that are located on the path connecting predetermined structural parts and participate in the connection. For example, in the case of -CH 2 -C(=O)-O-, the number of atoms constituting the linking group becomes 6, but the number of linking atoms becomes 3.
其中，RH1較佳為烴基，分別較佳為所述各碳數的烷基、烯基、芳基、芳烷基，更佳為烷基。於所述取代對苯二酚化合物中，藉由選擇烴基作為取代基RH1，可對本化合物賦予疏水性。藉此，可獲得所期望的蝕刻選擇性，故特佳。 Among them, R H1 is preferably a hydrocarbyl group, and each is preferably an alkyl group, an alkenyl group, an aryl group, and an aralkyl group of each carbon number, and more preferably an alkyl group. In the substituted hydroquinone compound, by selecting a hydrocarbon group as the substituent R H1 , hydrophobicity can be imparted to the compound. In this way, the desired etching selectivity can be obtained, which is particularly preferred.
m1表示1~4的整數，較佳為1~3的整數，更佳為1或2。 m1 represents an integer of 1 to 4, preferably an integer of 1 to 3, more preferably 1 or 2.
當m1為2以上時，多個RH1可形成環。此處，作為所形成的環，可列舉3員環至7員環，較佳為5員環或6員環。作為環結構的例子，可為芳香族環，亦可為脂肪族環。另外，可為烴環，亦可為雜環。其中，於本發明中，較佳為脂肪族環，更佳為烴的脂肪族環。具體而言，將對苯二酚骨架的C=C鍵視為雙鍵，可列舉：環己烯環、環戊烯環及環丁烯環等。 When m1 is 2 or more, a plurality of R H1 may form a ring. Here, as the formed ring, a 3-membered ring to a 7-membered ring may be mentioned, and a 5-membered ring or a 6-membered ring is preferable. As an example of the ring structure, it may be an aromatic ring or an aliphatic ring. In addition, it may be a hydrocarbon ring or a heterocyclic ring. Among them, in the present invention, an aliphatic ring is preferred, and a hydrocarbon aliphatic ring is more preferred. Specifically, the C=C bond of the hydroquinone skeleton is regarded as a double bond, and examples thereof include a cyclohexene ring, a cyclopentene ring, and a cyclobutene ring.
作為所述取代對苯二酚化合物的具體例，可列舉：2,5-二-第三丁基對苯二酚、2-第三丁基對苯二酚、2,5-二甲基對苯二酚、2-甲基對苯二酚等。 Specific examples of the substituted hydroquinone compound include: 2,5-di-tertiary butyl hydroquinone, 2-tertiary butyl hydroquinone, 2,5-dimethyl p-dihydroxybenzene Hydroquinone, 2-methylhydroquinone, etc.
取代對苯二酚化合物的ClogP值較佳為1以上，更佳為2以上，特佳為3.5以上。並不特別存在上限，但較實際的是10 以下。所謂ClogP值，是藉由計算於1-辛醇與水中的分配係數P的常用對數logP而求出的值。關於用於計算ClogP值的方法或軟體，可使用通常的方法或軟體，只要事先無特別說明，則於本發明中使用劍橋軟體(Cambridge soft)公司的ChemBioDraw Ultra 12.0中所編入的ClogP程式。藉由將取代對苯二酚化合物的ClogP值設為所述範圍，可使本化合物為疏水性，且獲得良好的蝕刻選擇性，故較佳。 The ClogP value of the substituted hydroquinone compound is preferably 1 or more, more preferably 2 or more, and particularly preferably 3.5 or more. There is no particular upper limit, but a more practical one is 10 the following. The so-called ClogP value is a value obtained by calculating the common logarithm logP of the partition coefficient P between 1-octanol and water. Regarding the method or software used to calculate the ClogP value, the usual method or software can be used. As long as there is no special description in advance, the ClogP program compiled in ChemBioDraw Ultra 12.0 of Cambridge soft is used in the present invention. By setting the ClogP value of the substituted hydroquinone compound in the above range, the compound can be made hydrophobic and good etching selectivity can be obtained, which is preferable.
於本發明中，於蝕刻液中，取代對苯二酚化合物的濃度較佳為10質量%以下，更佳為7質量%以下，進而更佳為5質量%以下，特佳為3質量%以下。作為下限，較佳為0.01質量%以上，更佳為0.05質量%以上，進而更佳為0.1質量%以上，特佳為0.5質量%以上。 In the present invention, the concentration of the substituted hydroquinone compound in the etching solution is preferably 10% by mass or less, more preferably 7% by mass or less, still more preferably 5% by mass or less, particularly preferably 3% by mass or less . The lower limit is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, still more preferably 0.1% by mass or more, and particularly preferably 0.5% by mass or more.
所述取代對苯二酚化合物可僅使用一種，亦可併用兩種以上。當併用兩種以上時，其併用比例並無特別限定，但合計使用量較佳為兩種以上的總和為所述濃度範圍。 Only one kind of the substituted hydroquinone compound may be used, or two or more kinds may be used in combination. When two or more are used in combination, the combined use ratio is not particularly limited, but the total amount of use is preferably such that the sum of two or more is the concentration range.
(有機溶媒) (Organic solvent)
於本發明的蝕刻液中可含有有機溶媒。其中，有機溶媒較佳為質子性極性有機溶媒(其中，當使用質子性極性有機溶媒時，並不妨礙與非質子性極性有機溶媒的組合使用)。作為質子性極性有機溶媒，可列舉醇化合物溶媒。其中，較佳為碳數1~36，更佳為2~24，進而更佳為4~18，特佳為4~12。有機溶媒較佳為醇化合物或醚化合物，其中更佳為醇化合物。作為具體例，可列舉 下述者。 The etching solution of the present invention may contain an organic solvent. Among them, the organic solvent is preferably a protic polar organic solvent (wherein, when a protic polar organic solvent is used, it does not prevent the use in combination with an aprotic polar organic solvent). Examples of the protic polar organic solvent include alcohol compound solvents. Among them, the carbon number is preferably from 1 to 36, more preferably from 2 to 24, even more preferably from 4 to 18, and particularly preferably from 4 to 12. The organic solvent is preferably an alcohol compound or an ether compound, and more preferably an alcohol compound. As a specific example, one can cite The following.
．醇化合物 . Alcohol compound
可列舉：甲醇、乙醇、1-丙醇、2-丙醇、2-丁醇、乙二醇、丙二醇、甘油、1,6-己二醇、環己二醇、山梨糖醇、木糖醇、聚乙二醇(二乙二醇及三乙二醇等)、聚丙二醇(二丙二醇及三丙二醇等)、2-甲基-2,4-戊二醇、1,3-丁二醇及1,4-丁二醇等。或者，作為伸烷基二醇單烷基醚，可列舉：乙二醇單甲基醚、乙二醇單乙基醚、乙二醇單丁基醚、丙二醇單甲基醚、二乙二醇單甲基醚、三乙二醇單甲基醚、四乙二醇單甲基醚、二丙二醇單甲基醚、三丙二醇單甲基醚、二乙二醇單丁基醚及二丙二醇單丁基醚等。 Examples include: methanol, ethanol, 1-propanol, 2-propanol, 2-butanol, ethylene glycol, propylene glycol, glycerin, 1,6-hexanediol, cyclohexanediol, sorbitol, xylitol , Polyethylene glycol (diethylene glycol and triethylene glycol, etc.), polypropylene glycol (dipropylene glycol and tripropylene glycol, etc.), 2-methyl-2,4-pentanediol, 1,3-butanediol and 1,4-Butanediol, etc. Or, as the alkylene glycol monoalkyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, diethylene glycol Monomethyl ether, triethylene glycol monomethyl ether, tetraethylene glycol monomethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, diethylene glycol monobutyl ether and dipropylene glycol monobutyl Base ether and so on.
其中，有機溶媒較佳為由下述式(O-1)所表示的化合物。 Among them, the organic solvent is preferably a compound represented by the following formula (O-1).
RO1-(-O-RO2-)n-ORO3…(O-1) R O1 -(-OR O2 -) n -OR O3 …(O-1)
．RO1及RO3 . R O1 and R O3
RO1及RO3分別獨立地為氫原子、碳數1~12(較佳為1~6，更佳為1~3)的烷基、碳數6~14(較佳為6~10)的芳基、或碳數7~15(較佳為7~11)的芳烷基。其中，RO3較佳為氫原子。 R O1 and R O3 are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms (preferably 1 to 6, more preferably 1 to 3), and carbon 6 to 14 (preferably 6 to 10) Aryl group or aralkyl group having 7 to 15 carbon atoms (preferably 7 to 11). Among them, R O3 is preferably a hydrogen atom.
．RO2 . R O2
RO2為碳數1以上、12以下的伸烷基。當存在多個RO2時，各RO2可不同。RO2較佳為碳數2~10，更佳為碳數2~6，特佳為 碳數2~4。RO2可為直鏈狀，亦可為分支狀，還可採取環結構。 R O2 is an alkylene group having 1 to 12 carbon atoms. When there are multiple RO2 , each RO2 may be different. R O2 preferably has a carbon number of 2 to 10, more preferably a carbon number of 2 to 6, and particularly preferably a carbon number of 2 to 4. R O2 can be linear or branched, and can also take a ring structure.
．n . n
n為0以上、12以下的整數，較佳為0以上、6以下。當n為2以上時，多個RO2可相互不同。再者，當n=0時，RO1及RO3不同時為氫原子。 n is an integer of 0 or more and 12 or less, preferably 0 or more and 6 or less. When n is 2 or more, a plurality of RO2 may be different from each other. Furthermore, when n=0, R O1 and R O3 are not hydrogen atoms at the same time.
RO1~RO3可相互連結而形成環。此處，作為所形成的環，可列舉3員環至7員環，較佳為5員環或6員環。例如，可列舉RO1及RO2連結而形成四氫呋喃結構或四氫吡喃結構，並於其中取代有-ORO3的化合物等。 R O1 to R O3 can be connected to each other to form a ring. Here, as the formed ring, a 3-membered ring to a 7-membered ring may be mentioned, and a 5-membered ring or a 6-membered ring is preferable. For example, a compound in which R O1 and R O2 are linked to form a tetrahydrofuran structure or a tetrahydropyran structure and substituted with -OR O3 , etc. can be mentioned.
於蝕刻液中，有機溶媒的濃度較佳為99質量%以下，更佳為98質量%以下，進而更佳為97質量%以下，特佳為96質量%以下。作為下限，較佳為50質量%以上，更佳為60質量%以上，進而佳為70質量%以上，進而更佳為80質量%以上，特佳為90質量%以上。藉由將有機溶媒設為所述範圍，可降低水的濃度。另一方面，可適當促進所述氟離子或取代對苯二酚化合物的作用並可實現使金屬層(第二層)的良好的蝕刻性與第一層或第三層的保護性並存，故較佳。 In the etching solution, the concentration of the organic solvent is preferably 99% by mass or less, more preferably 98% by mass or less, still more preferably 97% by mass or less, and particularly preferably 96% by mass or less. The lower limit is preferably 50% by mass or more, more preferably 60% by mass or more, still more preferably 70% by mass or more, still more preferably 80% by mass or more, and particularly preferably 90% by mass or more. By setting the organic solvent in the above range, the concentration of water can be reduced. On the other hand, the effect of the fluoride ion or the substituted hydroquinone compound can be appropriately promoted and the good etching properties of the metal layer (second layer) can be coexisted with the protective properties of the first or third layer. Better.
再者，於本發明中，所述有機溶媒可僅使用一種，亦可併用兩種以上。當併用兩種以上時，其併用比例並無特別限定，但合計使用量較佳為兩種以上的總和為所述濃度範圍。 Furthermore, in the present invention, only one type of the organic solvent may be used, or two or more types may be used in combination. When two or more are used in combination, the combined use ratio is not particularly limited, but the total amount of use is preferably such that the sum of two or more is the concentration range.
於本說明書中，當化合物、取代基、連結基等含有烷基、伸烷基、烯基、伸烯基、炔基及/或伸炔基時，該些可為環狀，亦 可為鏈狀，另外，可為直鏈，亦可進行分支，可由任意的基取代，亦可未經取代。此時，烷基、伸烷基、烯基、伸烯基、炔基及伸炔基可夾雜含有雜原子的基(例如O、S、CO及NRN等)，亦可伴隨於此而形成環結構。另外，當含有芳基、雜環基等時，該些可為單環，亦可為縮環，同樣地可經取代，亦可未經取代。 In this specification, when compounds, substituents, linking groups, etc. contain alkyl, alkylene, alkenyl, alkenylene, alkynyl and/or alkynylene, these may be cyclic or chain In addition, it may be linear or branched, and may be substituted with any group or unsubstituted. In this case, alkyl, alkylene, alkenyl, alkenylene, alkynyl and alkynylene groups may be interposed with heteroatom-containing groups (such as O, S, CO, NR N, etc.), and may be formed along with them.环结构。 Ring structure. In addition, when an aryl group, a heterocyclic group, etc. are contained, these may be a monocyclic ring or a condensed ring, and similarly may be substituted or unsubstituted.
所述RN為氫原子或取代基。作為取代基，較佳為烷基(碳數較佳為1~24，更佳為1~12，進而更佳為1~6，特佳為1~3)、烯基(碳數較佳為2~24，更佳為2~12，進而更佳為2~6，特佳為2~3)、炔基(碳數較佳為2~24，更佳為2~12，進而更佳為2~6，特佳為2~3)、碳數6~10的芳基及碳數7~11的芳烷基。 The RN is a hydrogen atom or a substituent. As the substituent, an alkyl group (the carbon number is preferably 1 to 24, more preferably 1 to 12, still more preferably 1 to 6, particularly preferably 1 to 3), alkenyl (the carbon number is preferably 2~24, more preferably 2~12, even more preferably 2~6, particularly preferably 2~3), alkynyl (the carbon number is preferably 2~24, more preferably 2~12, and still more preferably 2 to 6, particularly preferably 2 to 3), an aryl group with 6 to 10 carbons, and an aralkyl group with 7 to 11 carbons.
於本說明書中，至於以化合物的取代基及連結基的選擇項為首的溫度、厚度等各技術事項，可於其列表中分別獨立地記載，亦可相互組合。 In this specification, various technical items such as temperature, thickness, etc., including the options of the substituents of the compound and the linking group, may be separately described in the list, or may be combined with each other.
於本說明書中，當於末尾標註化合物或酸等來特定化合物時，於起到本發明的效果的範圍內，表示除所述化合物以外，亦包含其離子及鹽。另外，同樣地表示包含其衍生物。 In this specification, when a compound or acid is specified at the end, it means that in addition to the compound, its ion and salt are included in the range where the effect of the present invention is exerted. In addition, the same means that the derivative is included.
(水) (water)
於本發明的蝕刻液中較佳為含有水(水介質)。作為水(水介質)，可為於無損本發明的效果的範圍內含有溶解成分的水性介質、或者亦可含有不可避免的微量混合成分。其中，較佳為蒸餾水或離子交換水、或超純水等實施了淨化處理的水，特佳為使用半導體製造中所使用的超純水。水的濃度並無特別限定，但於蝕 刻液中，較佳為0.01質量%以上，更佳為0.1質量%以上，特佳為1質量%以上。作為上限，較佳為50質量%以下，更佳為35質量%以下，進而佳為15質量%以下，進而更佳為10質量%以下，特佳為5質量%以下。 The etching solution of the present invention preferably contains water (aqueous medium). As water (aqueous medium), it may be an aqueous medium containing dissolved components within a range that does not impair the effects of the present invention, or may contain unavoidable trace amounts of mixed components. Among them, distilled water, ion-exchanged water, or ultrapure water is preferably purified water, and it is particularly preferred to use ultrapure water used in semiconductor manufacturing. The concentration of water is not particularly limited, but due to corrosion In the etching solution, it is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and particularly preferably 1% by mass or more. As the upper limit, it is preferably 50% by mass or less, more preferably 35% by mass or less, still more preferably 15% by mass or less, still more preferably 10% by mass or less, particularly preferably 5% by mass or less.
於本發明中，較佳為將蝕刻液的水的濃度規定成既定的範圍。於不存在水的狀態下，有時不會充分地顯示出金屬層的蝕刻作用。就該觀點而言，較佳為應用水，藉由將其量抑制成適量，可抑制矽或鍺的層，進而其矽化物層及其他應保護的金屬層的損傷，故較佳。 In the present invention, it is preferable to set the concentration of water in the etching solution to a predetermined range. In the absence of water, the etching effect of the metal layer may not be fully exhibited. From this point of view, it is preferable to use water. By suppressing the amount to an appropriate amount, damage to the silicon or germanium layer, and the silicide layer and other metal layers to be protected can be suppressed, so it is preferable.
(界面活性劑) (Surfactant)
於本發明的蝕刻液中可含有界面活性劑。界面活性劑並無特別限定，可適宜應用陰離子性界面活性劑、陽離子性界面活性劑、非離子性界面活性劑、包含高分子化合物的界面活性劑、氟系界面活性劑或聚氧伸烷基系界面活性劑等。 The etching solution of the present invention may contain a surfactant. The surfactant is not particularly limited, and anionic surfactants, cationic surfactants, nonionic surfactants, surfactants containing polymer compounds, fluorine-based surfactants, or polyoxyalkylenes can be suitably used. Department of surfactants, etc.
相對於蝕刻液的總量，界面活性劑的濃度較佳為含有20質量%以下，更佳為10質量%以下，進而更佳為於1質量%以下的範圍內含有。作為下限值，較佳為含有0.001質量%以上，更佳為含有0.005質量%以上。界面活性劑可單獨使用一種，亦可將兩種以上組合使用。 The concentration of the surfactant relative to the total amount of the etching solution is preferably 20% by mass or less, more preferably 10% by mass or less, and still more preferably contained in the range of 1% by mass or less. As a lower limit, it is preferable to contain 0.001 mass% or more, and it is more preferable to contain 0.005 mass% or more. Surfactants can be used alone or in combination of two or more.
(pH調整劑) (pH adjuster)
於本發明的蝕刻液中，亦可使用pH調整劑。作為pH調整劑，為了提昇pH，可使用：四甲基銨及膽鹼等四級銨鹽、氫氧化鉀等 氫氧化鹼或鹼土鹽、2-胺基乙醇及胍等胺基化合物。為了降低pH，可列舉：碳酸、鹽酸、硝酸、硫酸、磷酸等無機酸，或甲酸、乙酸、丙酸、丁酸、戊酸、2-甲基丁酸、正己酸、3,3-二甲基丁酸、2-乙基丁酸、4-甲基戊酸、正庚酸、2-甲基己酸、正辛酸、2-乙基己酸、苯甲酸、乙醇酸、水楊酸、甘油酸、草酸、丙二酸、丁二酸、戊二酸、己二酸、庚二酸、順丁烯二酸、鄰苯二甲酸、蘋果酸、酒石酸、檸檬酸及乳酸等。 In the etching solution of the present invention, a pH adjuster can also be used. As a pH adjuster, in order to increase the pH, use: quaternary ammonium salts such as tetramethylammonium and choline, potassium hydroxide, etc. Amino compounds such as alkali hydroxide or alkaline earth salts, 2-aminoethanol and guanidine. In order to lower the pH, include: inorganic acids such as carbonic acid, hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, or formic acid, acetic acid, propionic acid, butyric acid, valeric acid, 2-methylbutanoic acid, n-hexanoic acid, 3,3-dimethyl Butyric acid, 2-ethylbutyric acid, 4-methylvaleric acid, n-heptanoic acid, 2-methylhexanoic acid, n-octanoic acid, 2-ethylhexanoic acid, benzoic acid, glycolic acid, salicylic acid, glycerin Acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, maleic acid, phthalic acid, malic acid, tartaric acid, citric acid, lactic acid, etc.
pH調整劑的使用量並無特別限定，只要以用於將pH調整成所述範圍所需的量使用即可。pH調整劑可單獨使用一種，亦可將兩種以上組合使用。 The amount of the pH adjuster used is not particularly limited, as long as it is used in an amount required to adjust the pH to the above-mentioned range. One kind of pH adjusting agent may be used alone, or two or more kinds may be used in combination.
(腐蝕電位) (Corrosion potential)
本發明的蝕刻液較佳為其腐蝕電位得到調節。具體而言，於藉由後述實施例中提示的測定方法所定義的腐蝕電位中，較佳為-0.25V以上，更佳為-0.2V以上，進而佳為-0.1V以上，進而更佳為0V以上，特佳為0.1V以上。作為上限，較實際的是0.5V以下。 The etching solution of the present invention preferably has its corrosion potential adjusted. Specifically, in the corrosion potential defined by the measurement method presented in the following examples, it is preferably -0.25V or more, more preferably -0.2V or more, still more preferably -0.1V or more, and still more preferably 0V or more, particularly preferably 0.1V or more. As the upper limit, it is more practical to be 0.5V or less.
(套組) (Set)
本發明中的蝕刻液可設為將其原料分割為多份而成的套組。例如，可列舉準備於水介質中含有所述氟離子的液組成物作為第1液，且準備於水介質中含有所述取代對苯二酚化合物的液組成物作為第2液的形態。作為其使用例，較佳為將兩液混合而對蝕刻液進行調製液體，然後適時地應用於所述蝕刻處理的形態。有機 溶媒等可含有任一種。藉由此種方式，可不會因取代對苯二酚化合物的分解導致液性能的劣化，且可有效地發揮所期望的蝕刻作用。第1液中的氟離子的濃度或第2液中的取代對苯二酚化合物的濃度可以事先敍述的1液的調配量為基礎，以混合後的濃度的形式進行適宜設定。 The etching liquid in this invention can be set as the set which divided the raw material into multiple parts. For example, a form in which a liquid composition containing the fluoride ion in an aqueous medium is prepared as the first liquid, and a liquid composition containing the substituted hydroquinone compound in the aqueous medium is prepared as the second liquid. As an example of its use, it is preferable to mix the two liquids to prepare the liquid for the etching liquid, and then to apply the liquid to the etching treatment in a timely manner. organic The solvent and the like may contain any of them. In this way, the degradation of the liquid performance due to the decomposition of the substituted hydroquinone compound is not caused, and the desired etching effect can be effectively exerted. The concentration of the fluoride ion in the first solution or the concentration of the substituted hydroquinone compound in the second solution can be appropriately set in the form of the concentration after mixing based on the previously described amount of blending in one solution.
(濃縮液) (Concentrate)
本發明的蝕刻液可作為濃縮液而準備。該情況下，當使用時，可利用水進行稀釋來使用。 The etching solution of the present invention can be prepared as a concentrated solution. In this case, when used, it can be diluted with water and used.
(容器) (container)
本發明的蝕刻液(不論是否為套組)只要腐蝕性等不成為問題，則可填充至任意的容器中來保管、搬運，然後使用。另外，面向半導體用途，較佳為容器的清潔度高、雜質的溶出少者。作為可使用的容器，可列舉愛塞璐化學(Aicello Chemical)(股份)製造的「清潔瓶(Clean Bottle)」系列、兒玉樹脂工業(Kodama Plastics)(股份)製造的「潔淨瓶(Pure Bottle)」(均為商品名)等，但並不限定於該些容器。 The etching solution of the present invention (regardless of whether it is a set or not) can be filled in any container, stored and transported, and then used as long as corrosiveness and the like are not a problem. In addition, for semiconductor applications, those with high cleanliness of the container and little elution of impurities are preferred. Examples of containers that can be used include the "Clean Bottle" series manufactured by Aicello Chemical (Co., Ltd.), and "Pure Bottle" manufactured by Kodama Plastics (Co., Ltd.). "(All product names), etc., but not limited to these containers.
(雜質、顆粒) (Impurities, particles)
本發明的蝕刻液鑒於其使用用途，較佳為液中的雜質，例如金屬成分等少。尤其，液中的Na、K及Ca離子濃度較佳為分別處於1ppt~1ppm(質量基準)的範圍內、或其以下。為了達成此種離子濃度，當準備本申請案的蝕刻液的構成成分(原材料)時，較佳為選擇金屬成分少的原材料，尤其，關於所述有機溶媒， 可推薦使用Na、K及Ca離子濃度分別為1ppt~1ppm(質量基準)的有機溶劑。後述的實施例的有機溶劑為該Na、K及Ca離子濃度處於範圍內者。 The etching solution of the present invention preferably has a small amount of impurities in the solution, for example, metal components, etc., in view of its intended use. In particular, the concentration of Na, K, and Ca ions in the liquid is preferably within the range of 1 ppt to 1 ppm (mass basis) or less. In order to achieve such an ion concentration, when preparing the constituent components (raw materials) of the etching solution of the present application, it is preferable to select a raw material with a small metal component. In particular, regarding the organic solvent, It is recommended to use organic solvents with Na, K, and Ca ion concentrations of 1ppt~1ppm (mass basis). The organic solvents of the examples described later are those whose Na, K, and Ca ion concentrations fall within the range.
另外，於蝕刻液中，平均粒徑為0.5μm以上的粗大粒子(顆粒)數較佳為處於100個/cm3以下的範圍內，更佳為處於50個/cm3以下的範圍內。 In addition, in the etching solution, the number of coarse particles (particles) having an average particle diameter of 0.5 μm or more is preferably in the range of 100 particles/cm 3 or less, and more preferably in the range of 50 particles/cm 3 or less.
[蝕刻條件] [Etching conditions]
作為蝕刻液的應用例，較佳為調製蝕刻液，其後適時地應用於所述蝕刻處理的形態。藉此，不會招致由各成分的分解所引起的液體性能的劣化，可使所期望的蝕刻作用有效地發揮。此處，所謂混合後「適時」，是指混合後至失去所期望的作用為止的時期，具體而言，較佳為60分鐘以內，更佳為30分鐘以內，進而更佳為10分鐘以內，特佳為1分鐘以內。並不特別存在下限，但較實際的是1秒以上。 As an application example of the etching solution, it is preferable to prepare the etching solution, and then to apply the etching solution in a timely manner. Thereby, deterioration of liquid performance due to decomposition of each component is not incurred, and the desired etching effect can be effectively exhibited. Here, the term "just in time" after mixing refers to the period after mixing until the desired effect is lost. Specifically, it is preferably within 60 minutes, more preferably within 30 minutes, and even more preferably within 10 minutes. Particularly best is within 1 minute. There is no particular lower limit, but it is more practical to be 1 second or more.
若使用圖3進行說明，則自噴出口13噴射所製備的蝕刻液，並應用於處理容器(處理槽)11內的半導體基板S的上表面。於該圖所示的實施形態中，自藥液供給口A供給藥液，並經由分岔點14及流路fc而轉移至噴出口13。流路fd表示用以再利用藥液的返回路徑。半導體基板S較佳為位於旋轉台12上，並藉由旋轉驅動部M而與旋轉台一同旋轉。再者，分岔點14可列舉作為切換閥的例子，可切換藥液的供給與返回來進行處理。或者，亦可應用同時進行藥液的供給與返回的可調節流通方向的閥。
3, the prepared etching liquid is sprayed from the
再者，本發明的蝕刻液鑒於其使用用途，較佳為液中的雜質，例如金屬成分等少。尤其，液中的Na、K及Ca各個的離子濃度較佳為處於1ppt~1ppm(質量基準)的範圍內。另外，於蝕刻液中，平均粒徑為0.5μm以上的粗大粒子數較佳為處於100個/cm3以下的範圍內，更佳為處於50個/cm3以下的範圍內。 Furthermore, the etching solution of the present invention preferably has a small amount of impurities in the solution, for example, metal components, etc., in view of its intended use. In particular, the ion concentration of each of Na, K, and Ca in the liquid is preferably in the range of 1 ppt to 1 ppm (mass basis). In addition, in the etching solution, the number of coarse particles having an average particle diameter of 0.5 μm or more is preferably in the range of 100 particles/cm 3 or less, and more preferably in the range of 50 particles/cm 3 or less.
於本發明中，較佳為使用單晶圓處理(single wafer processing)裝置。具體而言，單晶圓處理裝置較佳為具有處理槽，利用該處理槽搬送所述半導體基板或使其旋轉，向該處理槽內賦予(噴出、噴射、流下或滴加等)所述蝕刻液，而使所述蝕刻液接觸半導體基板者。 In the present invention, it is preferable to use a single wafer processing device. Specifically, the single-wafer processing apparatus preferably has a processing tank, and the semiconductor substrate is transported or rotated in the processing tank, and the etching is applied (ejected, sprayed, dripped, or dripped) into the processing tank. Liquid, and the etching liquid is brought into contact with the semiconductor substrate.
作為單晶圓處理裝置的優點，可列舉(i)始終供給新鮮的蝕刻液，因此再現性良好及(ii)面內均勻性高。進行線的溫度調節時的管理溫度較佳為設為與後述處理溫度相同的範圍。 The advantages of the single wafer processing device include (i) always supplying fresh etching liquid, so that the reproducibility is good and (ii) the in-plane uniformity is high. It is preferable that the management temperature during the temperature adjustment of the wire be set to the same range as the processing temperature described later.
單晶圓處理裝置較佳為於其處理槽中具備噴嘴，較佳為使該噴嘴於半導體基板的面方向搖擺來對半導體基板噴出蝕刻液的方法。藉此，可防止液體的劣化而較佳。另外，藉由設為套組而分為兩種液體以上，可使氣體等難以產生而較佳。 The single-wafer processing apparatus preferably has a nozzle in its processing tank, and preferably a method of swinging the nozzle in the surface direction of the semiconductor substrate to spray an etching solution to the semiconductor substrate. Thereby, deterioration of the liquid can be prevented, which is preferable. In addition, it is preferable to divide into two or more liquids as a set, which makes it difficult to generate gas or the like.
進行蝕刻的處理溫度較佳為10℃以上，更佳為20℃以上。作為上限，較佳為80℃以下，更佳為70℃以下，進而佳為60℃以下，進而更佳為50℃以下，特佳為40℃以下。藉由設為所述下限值以上，可確保對於第二層的充分的蝕刻速度而較佳。藉由設為所述上限值以下，可維持蝕刻處理速度的經時穩定性而較佳。 另外，可於室溫附近進行處理，藉此帶來能量消耗的削減。 The processing temperature for etching is preferably 10°C or higher, more preferably 20°C or higher. As the upper limit, it is preferably 80°C or lower, more preferably 70°C or lower, still more preferably 60°C or lower, still more preferably 50°C or lower, and particularly preferably 40°C or lower. By setting it as the above-mentioned lower limit or more, a sufficient etching rate with respect to the 2nd layer can be ensured, and it is preferable. By setting it as the upper limit or less, the time-dependent stability of the etching process rate can be maintained and it is preferable. In addition, the treatment can be performed near room temperature, thereby reducing energy consumption.
再者，蝕刻的處理溫度將後述實施例中所示的溫度測定方法中應用於基板的溫度作為基礎，但亦能夠以保存溫度來設定，或於利用批次處理進行管理的情況下以其槽內的溫度來設定，於利用循環系統進行管理的情況下以循環流路內的溫度來設定。 In addition, the etching processing temperature is based on the temperature applied to the substrate in the temperature measurement method shown in the following examples, but it can also be set with the storage temperature, or in the case of batch processing for management. The temperature inside is set, and when the circulation system is used for management, it is set with the temperature inside the circulation flow path.
蝕刻液的供給速度並無特別限定，但較佳為設為0.05L/min~5L/min，更佳為設為0.1L/min~3L/min。藉由設為所述下限值以上，可更良好地確保蝕刻的面內的均勻性而較佳。藉由設為所述上限值以下，可於連續處理時確保穩定的性能而較佳。當使半導體基板旋轉時，雖然取決於其大小等，但就與所述相同的觀點而言，較佳為以50rpm~1000rpm進行旋轉。 The supply rate of the etching solution is not particularly limited, but is preferably set to 0.05 L/min to 5 L/min, and more preferably set to 0.1 L/min to 3 L/min. By setting it as the said lower limit or more, the uniformity in the surface of an etching can be ensured more favorable, and it is preferable. By setting it as the upper limit or less, stable performance can be ensured during continuous processing, and it is preferable. When the semiconductor substrate is rotated, although it depends on its size, etc., from the same viewpoint as described above, it is preferable to rotate at 50 rpm to 1000 rpm.
於本發明的較佳的實施形態的單晶圓處理的蝕刻中，較佳為於既定的方向上搬送半導體基板或使其旋轉，於其空間內噴射蝕刻液來使所述蝕刻液接觸所述半導體基板。蝕刻液的供給速度或基板的旋轉速度與所述相同。 In the etching of the single-wafer processing in the preferred embodiment of the present invention, it is preferable to transport or rotate the semiconductor substrate in a predetermined direction, and spray an etching solution in the space to bring the etching solution into contact with the semiconductor substrate. Semiconductor substrate. The supply speed of the etching liquid or the rotation speed of the substrate is the same as described above.
於本發明的較佳的實施形態的單晶圓處理的裝置構成中，較佳為如圖4所示一面使噴出口(噴嘴)移動，一面賦予蝕刻液。具體而言，於本實施形態中，當針對半導體基板S應用蝕刻液時，使基板於r方向旋轉。另一方面，使噴出口沿著自半導體基板的中心部延伸至端部的移動軌跡線t移動。如上所述而於本實施形態中，將基板的旋轉方向與噴出口的移動方向設定成不同的方向，藉此兩者相互進行相對運動。其結果，可無遺漏地將蝕刻液賦予 至半導體基板的整個面上，而變成適宜地確保蝕刻的均勻性的構成。 In the structure of the single wafer processing apparatus according to the preferred embodiment of the present invention, it is preferable that the ejection port (nozzle) is moved while the etching solution is applied as shown in FIG. 4. Specifically, in this embodiment, when the etching liquid is applied to the semiconductor substrate S, the substrate is rotated in the r direction. On the other hand, the ejection port is moved along a movement trajectory line t extending from the center portion to the end portion of the semiconductor substrate. As described above, in this embodiment, the rotation direction of the substrate and the movement direction of the ejection port are set to different directions, whereby the two move relative to each other. As a result, the etching solution can be applied without omission To the entire surface of the semiconductor substrate, it becomes a configuration that appropriately ensures the uniformity of etching.
噴出口(噴嘴)的移動速度並無特別限定，但較佳為0.1cm/s以上，更佳為1cm/s以上。另一方面，作為其上限，較佳為30cm/s以下，更佳為15cm/s以下。移動軌跡線可為直線，亦可為曲線(例如圓弧狀)。於任一種情況下，移動速度均可根據實際的軌跡線的距離與其移動所耗費的時間來算出。1片基板的蝕刻所需要的時間較佳為10秒~300秒的範圍。 The moving speed of the ejection port (nozzle) is not particularly limited, but is preferably 0.1 cm/s or more, and more preferably 1 cm/s or more. On the other hand, as the upper limit, it is preferably 30 cm/s or less, and more preferably 15 cm/s or less. The movement trajectory line can be a straight line or a curve (for example, an arc shape). In either case, the moving speed can be calculated based on the actual distance of the trajectory line and the time it takes to move. The time required for etching one substrate is preferably in the range of 10 seconds to 300 seconds.
所述金屬層較佳為以高蝕刻速率來進行蝕刻。第二層(金屬層)的蝕刻速率[R2]並無特別限定，但考慮到生產效率，較佳為10Å/min以上，更佳為50Å/min以上，特佳為100Å/min以上。並不特別存在上限，但較實際的是1000Å/min以下。 The metal layer is preferably etched at a high etching rate. The etching rate [R2] of the second layer (metal layer) is not particularly limited, but in consideration of production efficiency, it is preferably 10 Å/min or more, more preferably 50 Å/min or more, and particularly preferably 100 Å/min or more. There is no particular upper limit, but it is more practical to be 1000 Å/min or less.
金屬層的露出範圍並無特別限定，但就本發明的優點變得更顯著的觀點而言，較佳為2nm以上，更佳為4nm以上。同樣地就效果的顯著性的觀點而言，上限值較實際的是1000nm以下，較佳為100nm以下，更佳為20nm以下。 The exposure range of the metal layer is not particularly limited, but from the viewpoint that the advantages of the present invention become more remarkable, it is preferably 2 nm or more, and more preferably 4 nm or more. Similarly, from the viewpoint of the significance of the effect, the upper limit is more practically 1000 nm or less, preferably 100 nm or less, and more preferably 20 nm or less.
第一層(矽層或鍺層)或第三層(矽化物層)的蝕刻速率[R1]並無特別限定，但較佳為不過度地去除，進而佳為100Å/min以下，進而更佳為60Å/min以下，特佳為40Å/min以下。並不特別存在下限，但若考慮測定極限，則較實際的是0.1Å/min以上。 The etching rate [R1] of the first layer (silicon layer or germanium layer) or the third layer (silicide layer) is not particularly limited, but it is preferably not excessively removed, and is more preferably 100 Å/min or less, and more preferably It is 60Å/min or less, particularly preferably 40Å/min or less. There is no particular lower limit, but if the measurement limit is considered, it is more practical to be 0.1 Å/min or more.
於第二層與第三層或第一層的選擇性蝕刻中，其蝕刻速率比([R2]/[R1])較佳為4以上，更佳為4.5以上，進而更佳為5 以上，特佳為5.5以上。上限並無特別規定，越高越佳，但較實際的是100以下，更實際的是50以下，特實際的是15以下。 In the selective etching of the second layer and the third layer or the first layer, the etching rate ratio ([R2]/[R1]) is preferably 4 or more, more preferably 4.5 or more, and even more preferably 5 Above, 5.5 or more is particularly preferred. The upper limit is not specifically specified, the higher the better, but the more practical is 100 or less, the more practical is 50 or less, and the more practical is 15 or less.
進而，於本發明的較佳的實施形態的蝕刻液中，亦可適宜地抑制Al或W等的金屬電極層，HfO、HfSiO、WO、AlOx、SiO2、SiOC、SiON、SiOCN、TiN、SiN或TiAlC等的絕緣膜層(有時將該些總稱為第四層)的損傷，因此應用於包含該些的半導體基板亦較佳。再者，於本說明書中，當藉由其元素的組合來表述金屬化合物的組成時，表示廣泛包含任意的組成者。例如，所謂SiOC(SiON)，表示Si與O及C(N)共存，並不表示其量的比率為1：1：1。此表示法於本說明書中通用，其他金屬化合物亦同樣如此。 Furthermore, in the etching solution of the preferred embodiment of the present invention, metal electrode layers such as Al or W, HfO, HfSiO, WO, AlO x , SiO 2 , SiOC, SiON, SiOCN, TiN, etc. can also be suitably suppressed. Insulating film layers such as SiN or TiAlC (sometimes collectively referred to as the fourth layer) are damaged, so it is also preferable to apply them to semiconductor substrates containing these. In addition, in this specification, when the composition of a metal compound is expressed by a combination of its elements, it means that any composition is widely included. For example, the so-called SiOC (SiON) means the coexistence of Si, O and C (N), and does not mean that the ratio of the amounts thereof is 1:1:1. This notation is commonly used in this specification, and the same is true for other metal compounds.
一片基板的蝕刻所需要的時間較佳為10秒以上，更佳為50秒以上。作為上限，較佳為300秒以下，更佳為200秒以下。 The time required for the etching of one substrate is preferably 10 seconds or more, and more preferably 50 seconds or more. As the upper limit, it is preferably 300 seconds or less, and more preferably 200 seconds or less.
[半導體基板製品的製造] [Manufacturing of semiconductor substrate products]
於本實施形態中，較佳為經由如下的步驟來製造具有所期望的結構的半導體基板製品：於矽晶圓上形成所述矽層與金屬層來製成半導體基板的步驟；對所述半導體基板進行退火的步驟；將蝕刻液賦予至半導體基板上，使蝕刻液與金屬層接觸，並選擇性地去除所述金屬層的步驟。此時，於蝕刻中使用所述特定的蝕刻液。所述步驟的順序並不限制地進行解釋，亦可於各個步驟間進而包含其他步驟。 In this embodiment, it is preferable to manufacture a semiconductor substrate product with a desired structure through the following steps: a step of forming the silicon layer and a metal layer on a silicon wafer to make a semiconductor substrate; The step of annealing the substrate; the step of applying an etching solution to the semiconductor substrate, bringing the etching solution into contact with the metal layer, and selectively removing the metal layer. At this time, the specific etching solution is used for etching. The sequence of the steps is not limitedly interpreted, and other steps may be included between each step.
晶圓尺寸並無特別限定，可適宜地使用直徑為8吋、直徑為 12吋、或直徑為14吋者(1吋=25.4mm)。 The wafer size is not particularly limited, it can be suitably used with a diameter of 8 inches and a diameter of 12 inches or 14 inches in diameter (1 inch = 25.4mm).
再者，當於本說明書中談及「準備」時，表示除對特定的材料進行合成或調配等來準備以外，亦包含藉由購入等來籌措既定的物質。另外，於本說明書中，將以對半導體基板的各材料進行蝕刻的方式使用蝕刻液稱為「應用」，但其實施形態並無特別限定。例如，廣泛包含使蝕刻液與基板接觸，具體而言，可利用批次式裝置進行浸漬來進行蝕刻，亦可利用單晶圓處理裝置藉由噴出來進行蝕刻。 Furthermore, when talking about "preparation" in this manual, it means not only preparing specific materials by synthesizing or blending them, but also including purchasing predetermined materials. In addition, in this specification, the use of the etchant to etch each material of the semiconductor substrate is referred to as "application", but the embodiment is not particularly limited. For example, it is widely included that the etching solution is brought into contact with the substrate. Specifically, etching can be performed by immersion using a batch type device, or etching can be performed by spraying using a single wafer processing device.
於本說明書中，所謂半導體基板，是以不僅包含晶圓，而且包含在其中施加有電路結構的基板結構體整體的含義來使用。所謂半導體基板構件，是指構成所述定義的半導體基板的構件，可包含一種材料，亦可包含多種材料。再者，有時將加工完的半導體基板作為半導體基板製品來區別稱呼，視需要進一步進行區別，將對其進行加工並切割後取出的晶片及其加工製品稱為半導體元件。即，半導體元件或組裝有半導體元件的半導體製品廣義上屬於半導體基板製品。 In this specification, the term "semiconductor substrate" is used to include not only the wafer but also the entire substrate structure to which the circuit structure is applied. The term "semiconductor substrate member" refers to a member constituting the semiconductor substrate defined above, and may include one material or multiple materials. In addition, the processed semiconductor substrate is sometimes referred to as a semiconductor substrate product, and further distinctions are made if necessary, and the wafers and processed products taken out after processing and dicing are referred to as semiconductor elements. That is, semiconductor elements or semiconductor products incorporating semiconductor elements are broadly classified as semiconductor substrate products.
[實施例] [Example]
以下，列舉實施例來更詳細地說明本發明，但本發明並不限定於以下的實施例。再者，只要事先無特別說明，實施例中作為配方或調配量所示的%及份為質量基準。 Hereinafter, the present invention will be explained in more detail with examples, but the present invention is not limited to the following examples. In addition, as long as there is no special description in advance, the% and parts shown as the formula or the compounding amount in the examples are the mass basis.
[實施例1．比較例1] [Example 1. Comparative example 1]
(試驗基板的製作) (Production of test board)
使Si膜於市售的矽基板(直徑：12吋)上磊晶成長，並以厚度為500Å(50nm)的膜厚形成。進而，藉由CVD(chemical vapor deposition)而於所述Si磊晶層上形成Ti的層。於800℃下對其進行10秒退火，形成矽化物層來作為試驗基板。退火後的矽化物層的厚度為15nm，金屬層的厚度為5nm。 The Si film was epitaxially grown on a commercially available silicon substrate (diameter: 12 inches) and formed with a film thickness of 500 Å (50 nm). Furthermore, a Ti layer is formed on the Si epitaxial layer by CVD (chemical vapor deposition). It was annealed at 800°C for 10 seconds to form a silicide layer as a test substrate. The thickness of the annealed silicide layer is 15 nm, and the thickness of the metal layer is 5 nm.
準備其他膜亦以相同方式藉由CVD等來製成的毯覆晶圓(blanket wafer)。於下表的試驗中，使用該些各試驗晶圓測定各層的蝕刻速度。 Other films are also prepared by CVD in the same way as blanket wafers. In the tests in the following table, the etching rates of each layer were measured using these test wafers.
(蝕刻試驗) (Etching test)
利用單晶圓處理裝置(SPS-歐洲(SPS-Europe)B.V.公司製造的保羅斯(POLOS)(商品名))，於下述的條件下對所述空白晶圓及試驗用基板進行蝕刻，並實施評價試驗。 Using a single wafer processing device (POLOS (trade name) manufactured by SPS-Europe BV), the blank wafer and test substrate were etched under the following conditions, and Implement evaluation tests.
．處理溫度：24℃室溫 . Processing temperature: 24℃ room temperature
．供給速度：1L/min. . Supply speed: 1L/min.
．晶圓轉速：500rpm . Wafer speed: 500rpm
．噴嘴移動速度：7cm/S . Nozzle moving speed: 7cm/S
再者，蝕刻液的供給以一種液體來進行(使用圖3的A線)。各處理試驗於調製液體後立即進行。 Furthermore, the supply of the etching liquid is performed with one liquid (using the line A in FIG. 3). Each treatment test was carried out immediately after the liquid was prepared.
(處理溫度的測定方法) (Method of measuring processing temperature)
將堀場製作所股份有限公司製造的放射溫度計IT-550F(商品名)固定於所述單晶圓處理裝置內的晶圓上30cm的高度處。使溫度計朝向自晶圓中心起2cm外側的晶圓表面上，一面流入藥液 一面測量溫度。自放射溫度計進行數位輸出，並利用個人電腦連續地記錄溫度。其中，將對溫度穩定的10秒的溫度進行平均所得的值設為晶圓上的溫度。 A radiation thermometer IT-550F (trade name) manufactured by Horiba Manufacturing Co., Ltd. was fixed at a height of 30 cm on the wafer in the single wafer processing apparatus. Place the thermometer on the surface of the wafer 2cm outside from the center of the wafer, and flow the chemical solution into it Measure the temperature on one side. The self-radiation thermometer performs digital output and uses a personal computer to continuously record the temperature. Here, the value obtained by averaging the temperature for 10 seconds at which the temperature is stable is the temperature on the wafer.
(蝕刻速度[ER]) (Etching speed [ER])
關於蝕刻速度(ER)，藉由利用橢圓偏光法(使用分光橢圓儀，J.A.伍拉姆日本(J.A.Woollam JAPAN)股份有限公司的瓦賽(Vase)商品名))測定蝕刻處理前後的膜厚來算出。採用5點的平均值(測定條件測定範圍：1.2eV-2.5eV，測定角：70度、75度)。將各層的蝕刻速度的測定結果示於下表中。 Regarding the etching rate (ER), the film thickness before and after the etching process was measured by the ellipsometry (using a spectroscopic ellipsometer, JA Woollam Japan (JAWoollam JAPAN) Co., Ltd.'s Vase brand name). Figure out. An average value of 5 points is used (measurement condition measurement range: 1.2eV-2.5eV, measurement angle: 70 degrees, 75 degrees). The measurement results of the etching rate of each layer are shown in the following table.
[表1]
<表的註釋> <Notes to Table>
DGMBE：二乙二醇單丁基醚 DGMBE: Diethylene glycol monobutyl ether
EGMBE：乙二醇單丁基醚 EGMBE: ethylene glycol monobutyl ether
EGMEE：乙二醇單乙基醚 EGMEE: ethylene glycol monoethyl ether
TiSi：矽化鈦矽 TiSi: Titanium Silicide
調配量：質量份 Allocation amount: parts by mass
成分(A)：氟離子源 Ingredient (A): Fluoride ion source
成分(B)：水 Ingredient (B): water
成分(C)：有機溶媒(質子性極性有機溶媒) Component (C): organic solvent (protic polar organic solvent)
成分(D)：取代對苯二酚化合物等 Ingredient (D): Substituted hydroquinone compounds, etc.
<腐蝕電位的測定方法> <Measurement method of corrosion potential>
裝置：普林斯頓應用研究(Princeton Applied Research)公司型號為263A(商品名) Device: Princeton Applied Research (Princeton Applied Research) company model is 263A (trade name)
基板：利用5%HF進行30sec處理，並去除了表面的自然氧化膜的Si基板(P型，1Ω．cm~35Ω．cm) Substrate: A Si substrate (P type, 1Ω·cm~35Ω·cm) treated with 5%HF for 30sec, and the natural oxide film on the surface is removed
利用H2O 5質量%+溶劑(二乙二醇單丁基醚)+NaClO4 0.1質量%+氧化劑0.08mol/kg的藥液測定腐蝕電位。 The corrosion potential was measured using a chemical solution of H 2 O 5 mass% + solvent (diethylene glycol monobutyl ether) + NaClO 4 0.1 mass% + oxidant 0.08 mol/kg.
具體而言，利用將H2O 5質量%、溶劑(二乙二醇單丁基醚)殘部、NaClO4 0.1質量%、及氧化劑0.08mol/kg混合而成的藥液測定腐蝕電位。此處，過氯酸鈉作為利用溶劑系的測定中的支持電解質而添加。測定程序如下所述。 Specifically, the corrosion potential was measured using a chemical solution prepared by mixing H 2 O 5 mass %, solvent (diethylene glycol monobutyl ether) residue, NaClO 4 0.1 mass %, and oxidizing agent 0.08 mol/kg. Here, sodium perchlorate is added as a supporting electrolyte in the measurement using a solvent system. The measurement procedure is as follows.
1.夾持實施了特定前處理的基板(測定材料)作為作用電極 (Working electrode)。 1. Clamp the substrate (measurement material) that has been subjected to specific pretreatment as a working electrode (Working electrode).
2.夾持填充有飽和KCl/AgCl溶液的Ag/AgCl參照電極作為參照電極(Reference electrode)。 2. Clamp the Ag/AgCl reference electrode filled with a saturated KCl/AgCl solution as a reference electrode.
3.夾持鉑相對電極：普林斯頓應用研究公司製造的TCE-1作為相對電極(Counter electrode)。 3. Clamping platinum counter electrode: TCE-1 manufactured by Princeton Applied Research Co., Ltd. is used as a counter electrode.
4.將測定溶液加入至單元中。 4. Add the measurement solution to the cell.
5.開始測定。 5. Start the measurement.
(1)以線性掃描(linear sweep)模式選擇塔伏曲線(Tafel plot)。 (1) Select the Tafel plot in linear sweep mode.
(2)以於開路電位(Open circuit potential)±0.5V下進行掃描的方式設定。 (2) It is set to scan under the open circuit potential (Open circuit potential) ±0.5V.
6.根據V-I圖表讀取腐蝕電位。 6. Read the corrosion potential according to the V-I chart.
如根據所述表的結果而可知般，可知根據本發明的蝕刻液，Ti的蝕刻速率高，並可將矽化物層(TiSi)的蝕刻速率抑制得低。另外，可確認對於應用於半導體基板的其他各金屬化合物材料亦可實現適宜的保護性。 As can be seen from the results of the table, it can be seen that according to the etching solution of the present invention, the etching rate of Ti is high, and the etching rate of the silicide layer (TiSi) can be suppressed to be low. In addition, it can be confirmed that suitable protective properties can also be achieved for other metal compound materials applied to semiconductor substrates.
對本發明及該實施方式一併加以說明，但我們認為只要無特別指定，則在說明的任何細節部分中都不對我們的發明作出限定，應並不違背隨附的申請專利範圍中所示的發明的精神與範圍地廣泛地進行解釋。 The present invention and the implementation are described together, but we believe that as long as there is no special designation, any details of the description will not limit our invention, and it should not violate the invention shown in the scope of the attached patent application. The spirit and scope of the interpreter are broadly explained.
本申請案主張基於2015年2月23日於日本提出專利申請的日本專利特願2015-032597的優先權，該些內容於此進行參 照而將其內容作為本說明書的記載的一部分而併入於本申請案中。 This application claims priority based on Japanese Patent Application No. 2015-032597 filed in Japan on February 23, 2015, and these contents are referred to here. The content is incorporated in this application as a part of the description of this specification.
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