TWI524411B

TWI524411B - A group iii-v compound semiconductor wafer and method for cleaning the same

Info

Publication number: TWI524411B
Application number: TW101117405A
Authority: TW
Inventors: 王冰; 李海淼; 徐衛; 劉文森
Original assignee: 北京通美晶體技術有限公司
Priority date: 2011-05-16
Filing date: 2012-05-16
Publication date: 2016-03-01
Also published as: CN102789964B; CN102789964A; TW201301378A

Description

III-V族化合物半導體晶圓及其清洗方法 III-V compound semiconductor wafer and cleaning method thereof

本發明涉及一種III-V族化合物半導體晶圓及其清洗方法。 The invention relates to a III-V compound semiconductor wafer and a cleaning method thereof.

隨著半導體雷射器、光纖通信用光接收元件、高速和高頻半導體元件製造技術的發展，對III-V族化合物半導體材料(例如砷化鎵、磷化銦等)的清潔度，特別是其表面清潔度的要求越來越高。 With the development of semiconductor lasers, optical communication components for optical communication, and high-speed and high-frequency semiconductor device manufacturing technologies, the cleanliness of III-V compound semiconductor materials (such as gallium arsenide, indium phosphide, etc.), especially The requirements for surface cleanliness are getting higher and higher.

對於半導體晶圓的主要應用而言，其表面的主要污染物是顆粒和金屬離子。 For the main applications of semiconductor wafers, the main contaminants on the surface are particles and metal ions.

對於另一類半導體晶圓矽晶圓，已經有了一套通用的清洗方法，即Kern和Puotinen提出的RCA方法(RCA Review,vol.31,pp.187-206,June,1970)。該方法用氨水、雙氧水水溶液(SC-1)清洗顆粒，用鹽酸、雙氧水水溶液(SC-2)去除金屬。 For another type of semiconductor wafer wafer, there is a common cleaning method, the RCA method proposed by Kern and Puotinen (RCA Review, vol. 31, pp. 187-206, June, 1970). In this method, the particles are washed with aqueous ammonia and aqueous hydrogen peroxide (SC-1), and the metal is removed with hydrochloric acid and aqueous hydrogen peroxide (SC-2).

然而，III-V族化合物半導體材料，例如磷化銦半導體材料，由於屬於二元化合物，使得其晶圓表面的反應特性與矽晶圓不相同，因此不能套用矽晶圓的清洗方法。特別是，上述RCA還具有如下缺點：雖然SC-1溶液能夠基本上除去半導體晶圓表面的顆粒物，但卻同時又給其帶來了另外的外來金屬污染源。儘管通過後一步SC-2 溶液處理有可能降低晶圓表面上外來金屬雜質的濃度，但該處理的結果是使粘附在晶圓上的顆粒物再次增加(P.H.Singer,Semiconductor International,pp.36-39,December,1992)。此外，由於有些地方腐蝕清洗過快，而有些地方還沒有被腐蝕清洗，因而造成晶圓表面腐蝕不均勻。這種晶圓不能理想地用於後續的磊晶生長。 However, III-V compound semiconductor materials, such as indium phosphide semiconductor materials, are binary compounds, so that the reaction characteristics of the wafer surface are different from those of the germanium wafer, so the cleaning method of the germanium wafer cannot be applied. In particular, the above RCA also has the disadvantage that although the SC-1 solution is capable of substantially removing particulate matter from the surface of the semiconductor wafer, it also brings additional sources of foreign metal contamination. Despite the latter step SC-2 Solution treatment has the potential to reduce the concentration of foreign metal impurities on the wafer surface, but the result of this treatment is to increase the amount of particulate matter adhering to the wafer (P.H. Singer, Semiconductor International, pp. 36-39, December, 1992). In addition, due to corrosion cleaning in some places, and some areas have not been corroded and cleaned, the surface of the wafer is not corroded unevenly. Such wafers are not ideal for subsequent epitaxial growth.

中國專利CN101661869中描述了一種清洗砷化鎵(III-V族化合物)半導體晶圓的方法，其包括在超音波作用下用清洗劑處理、分別用濃硫酸和NH₄OH-H₂O₂溶液清洗砷化鎵晶圓。該方法沒有有效地清除金屬殘留並且清洗過的砷化鎵晶圓表面腐蝕嚴重，所以也不能簡單套用該法來清洗其他III-V族化合物半導體晶圓，特別是磷化銦半導體晶圓。 A method for cleaning a gallium arsenide (III-V compound) semiconductor wafer is described in Chinese patent CN101661869, which comprises treating with a cleaning agent under ultrasonic action, respectively using concentrated sulfuric acid and NH ₄ OH-H ₂ O ₂ solution. Clean the gallium arsenide wafer. This method does not effectively remove metal residues and the surface of the cleaned gallium arsenide wafer is severely corroded, so it is not easy to apply this method to clean other III-V compound semiconductor wafers, especially indium phosphide semiconductor wafers.

因此，現有技術中的方法很難較好地去除III-V族化合物半導體材料(例如磷化銦半導體材料)晶圓表面的顆粒和金屬殘留物，同時還能保證晶圓表面的腐蝕均勻性。 Therefore, the prior art method is difficult to remove particles and metal residues on the surface of the III-V compound semiconductor material (for example, indium phosphide semiconductor material), and at the same time, to ensure the uniformity of the surface of the wafer.

本發明提供一種清洗III-V族化合物半導體晶圓的方法，該方法包括以下步驟：(1)用一種濃酸於不低於50℃處理晶圓；(2)用一種濃酸於不高於30℃處理晶圓；(3)用高純水洗滌晶圓； (4)用一種有機酸溶液處理晶圓；(5)用高純水洗滌晶圓；(6)用一種NH₄OH-H₂O₂溶液處理晶圓；(7)用高純水洗滌晶圓；以及(8)乾燥所得晶圓。 The invention provides a method for cleaning a III-V compound semiconductor wafer, the method comprising the steps of: (1) treating a wafer with a concentrated acid at not lower than 50 ° C; (2) using a concentrated acid at not higher than Processing wafers at 30 ° C; (3) washing wafers with high purity water; (4) treating wafers with an organic acid solution; (5) washing wafers with high purity water; (6) using a NH ₄ OH-H ₂ O ₂ solution Processing the wafer; (7) washing the wafer with high purity water; and (8) drying the resulting wafer.

本發明的方法不但能夠有效地減少晶圓表面的顆粒和金屬殘留，同時還能提高晶圓表面的腐蝕均勻性，使白霧值(haze value)降低，從而達到改善晶圓表面的光點缺陷的效果。 The method of the invention can not only effectively reduce the particle and metal residue on the surface of the wafer, but also improve the corrosion uniformity of the surface of the wafer and reduce the haze value, thereby improving the spot defect on the surface of the wafer. Effect.

因此，本發明還提供一種III-V族化合物半導體晶圓，其特徵在於，每平方公分晶圓表面面積中大於0.11 μm²的顆粒≦0.5顆(按統計數除以晶圓表面積計)，晶圓表面的金屬殘留Cu≦10×10¹⁰原子/cm²且Zn≦10×10¹⁰原子/cm²，表面平均白霧值≦1.0 ppm。 Therefore, the present invention also provides a III-V compound semiconductor wafer characterized in that, in a surface area of more than 0.11 μm ² per square centimeter of wafer surface area, 0.5 particles (by statistical division divided by wafer surface area), crystal The metal residue on the round surface was Cu ≦ 10 × 10 ¹⁰ atoms/cm ² and Zn ≦ 10 × 10 ¹⁰ atoms/cm ² , and the surface average white fog value was 1.0 ppm.

本發明提供一種清洗III-V族化合物半導體晶圓方法，包括以下步驟：(1)用一種濃酸於不低於50℃處理晶圓；(2)用一種濃酸於不高於30℃處理晶圓；(3)用高純水洗滌晶圓；(4)用一種有機酸溶液處理晶圓；(5)用高純水洗滌晶圓； (6)用一種NH₄OH-H₂O₂溶液處理晶圓；(7)用高純水洗滌晶圓；以及(8)乾燥所得晶圓。 The invention provides a method for cleaning a III-V compound semiconductor wafer, comprising the steps of: (1) treating a wafer with a concentrated acid at not lower than 50 ° C; (2) treating with a concentrated acid at not higher than 30 ° C Wafer; (3) washing the wafer with high purity water; (4) treating the wafer with an organic acid solution; (5) washing the wafer with high purity water; (6) treating the wafer with a NH ₄ OH-H ₂ O ₂ solution (7) washing the wafer with high purity water; and (8) drying the resulting wafer.

出乎意料的是，本發明的方法不但能使晶圓表面獲得有效的清洗，減少晶圓表面顆粒並顯著降低金屬、特別是銅、鋅的殘留量，而且還能同時保證腐蝕的均勻性，使得白霧值更低。因此，使用本發明方法獲得的晶圓能夠很好地作為磊晶基材使用。 Unexpectedly, the method of the present invention not only enables effective cleaning of the wafer surface, reduces wafer surface particles and significantly reduces the residual amount of metals, especially copper and zinc, but also ensures the uniformity of corrosion. Make the white fog value lower. Therefore, the wafer obtained by the method of the present invention can be suitably used as an epitaxial substrate.

本發明方法中，作為原始晶圓使用的晶圓(即步驟(1)使用的晶圓)是已經完成機械化學拋光和化學精細拋光的晶圓(即已經完成精細鏡面拋光的晶圓)，通常是單面拋光後的晶圓，其拋光面表面微觀粗糙度Ra0.5 nm(用AFM(原子力顯微鏡)測試)，優選Ra0.3 nm。如果要求兩面拋光，則上述參數為兩面的平均值。 In the method of the present invention, the wafer used as the original wafer (ie, the wafer used in the step (1)) is a wafer that has been subjected to mechanochemical polishing and chemical fine polishing (ie, a wafer that has been finished with fine mirror polishing), usually Is a single-sided polished wafer with a micro-roughness Ra of the polished surface 0.5 nm (tested by AFM (atomic force microscope)), preferably Ra 0.3 nm. If both sides are required to be polished, the above parameters are the average of the two sides.

在本發明方法的步驟(1)(用一種濃酸於不低於50℃處理晶圓)中，優選地，所述濃酸為無機酸，包括，但不限於，硫酸、鹽酸、磷酸和硝酸等，優選硝酸或硫酸。因為在一定的溫度下，不同酸的溶解性不同，所以採用不同的酸時，均採用其在處理溫度下的濃酸，例如其濃度為其相應溫度時的飽和濃度的60%以上時，則認為其為「濃酸」。優選地，採用硫酸時，其濃度C₁通常不小於65重量%。通常，所用硫酸濃度為65-98重量%，優選70-97重量%。處理溫度T₁通常為50-80℃，優選55-75℃，更優選60-70℃。只要滿足溫度不低於50℃的條件，該處理步驟中的溫度可以變化。該步驟的處理時間P₁通常為1-20秒，優選為2-18秒，更優選為3-15秒。所述處理包括，但不限於，沖洗和浸入等，優選浸入處理。在處理過程中，優選採用百萬頻率超音波(mega-sonic)或超音波(ultrasonic)處理。 In the step (1) of the method of the present invention (processing a wafer with a concentrated acid at not lower than 50 ° C), preferably, the concentrated acid is a mineral acid including, but not limited to, sulfuric acid, hydrochloric acid, phosphoric acid, and nitric acid. Etc., preferably nitric acid or sulfuric acid. Since the solubility of different acids is different at a certain temperature, when different acids are used, the concentrated acid at the treatment temperature is used, for example, when the concentration is 60% or more of the saturated concentration at the corresponding temperature, It is considered to be "concentrated acid". Preferably, when sulfuric acid is used, its concentration C ₁ is usually not less than 65% by weight. Usually, the concentration of sulfuric acid used is from 65 to 98% by weight, preferably from 70 to 97% by weight. The treatment temperature T ₁ is usually from 50 to 80 ° C, preferably from 55 to 75 ° C, more preferably from 60 to 70 ° C. The temperature in the treatment step may vary as long as the temperature is not lower than 50 °C. The treatment time P _{1 of} this step is usually from 1 to 20 seconds, preferably from 2 to 18 seconds, more preferably from 3 to 15 seconds. The treatment includes, but is not limited to, rinsing and immersion, etc., preferably immersion treatment. During processing, it is preferred to use mega-sonic or ultrasonic processing.

在本發明方法的步驟(2)(用一種濃酸於不高於30℃處理晶圓)中，優選地，所述濃酸為無機酸，包括，但不限於，硫酸、鹽酸、磷酸和硝酸等，優選硝酸或硫酸。因為在一定的溫度下，不同酸的溶解性不同，所以採用不同的酸時，均採用其在處理溫度下的濃酸，例如其濃度為其相應溫度時的飽和濃度的60%以上時，則認為其為「濃酸」。優選地，採用硫酸時，其濃度C₂通常不小於65重量%。通常，所用硫酸濃度為65-98重量%，優選70-97重量%。處理溫度T₂通常不高於30℃，優選不高於25℃。只要滿足溫度不高於30℃的條件，該處理步驟中的溫度可以變化。通常，處理溫度為5-30℃，優選8-28℃，更優選10-25℃。該步驟的處理時間P₂通常為0.5-15秒，優選1-12秒，更優選2-10秒。所述處理包括，但不限於，沖洗和浸入等，優選浸入處理。在處理過程中，優選採用百萬頻率超音波或超音波處理。 In step (2) of the method of the invention (processing the wafer with a concentrated acid at not higher than 30 ° C), preferably, the concentrated acid is a mineral acid including, but not limited to, sulfuric acid, hydrochloric acid, phosphoric acid and nitric acid Etc., preferably nitric acid or sulfuric acid. Since the solubility of different acids is different at a certain temperature, when different acids are used, the concentrated acid at the treatment temperature is used, for example, when the concentration is 60% or more of the saturated concentration at the corresponding temperature, It is considered to be "concentrated acid". Preferably, when sulfuric acid is used, its concentration C ₂ is usually not less than 65% by weight. Usually, the concentration of sulfuric acid used is from 65 to 98% by weight, preferably from 70 to 97% by weight. The treatment temperature T ₂ is usually not higher than 30 ° C, preferably not higher than 25 ° C. The temperature in the treatment step may vary as long as the temperature is not higher than 30 °C. Usually, the treatment temperature is 5 to 30 ° C, preferably 8 to 28 ° C, more preferably 10 to 25 ° C. The treatment time P _{2 of} this step is usually from 0.5 to 15 seconds, preferably from 1 to 12 seconds, more preferably from 2 to 10 seconds. The treatment includes, but is not limited to, rinsing and immersion, etc., preferably immersion treatment. In the course of processing, it is preferred to use a million frequency ultrasonic or ultrasonic processing.

優選地，步驟(1)和(2)採用相同的酸進行處理。此時，可以採用同一份濃酸，按照不同的溫度連續處理，即在完成第一步處理之後，迅速降溫至第二步的處理溫度繼續處理；在這種實施方案中，C₂為步驟(2)開始時的濃度。如果第二步所用的酸與第一步所用的酸不同，則在第一步酸處理(1)之後，優選地，晶圓用高純水洗滌5-30秒之後再進行第二步的酸處理(2)。 Preferably, steps (1) and (2) are treated with the same acid. At this time, the same concentrated acid can be used, and the treatment is continuously performed according to different temperatures, that is, after the first step of treatment is completed, the temperature is rapidly cooled to the processing temperature of the second step to continue the treatment; in this embodiment, C ₂ is the step ( 2) The concentration at the beginning. If the acid used in the second step is different from the acid used in the first step, after the first acid treatment (1), preferably, the wafer is washed with high-purity water for 5-30 seconds before the second step of acid treatment ( 2).

在本發明的一個特別優選的實施方案中，步驟(1)的酸的濃度C₁、處理溫度T₁和處理時間P₁與步驟(2)的酸的濃度C₂、處理溫度T₂和處理時間P₂之間滿足以下關係：C₂×P₂×(T₂+273.15)≦C₁×P₁×(T₁+273.15)≦3×C₂×P₂×(T₂+273.15)，以上各式中，濃度單位為重量百分比濃度，處理溫度為攝氏度，處理時間為秒。 In a particularly preferred embodiment of the invention, the acid concentration C _{1 of the} step (1), the treatment temperature T ₁ and the treatment time P ₁ and the acid concentration C _{2 of the} step (2), the treatment temperature T ₂ and the treatment The following relationship is satisfied between times P ₂ : C ₂ × P ₂ × (T ₂ + 273.15) ≦ C ₁ × P ₁ × (T ₁ + 273.15) ≦ 3 × C ₂ × P ₂ × (T ₂ + 273.15), In the above formulas, the concentration unit is a weight percentage concentration, the treatment temperature is Celsius, and the treatment time is seconds.

進一步優選的是，步驟(1)的酸的濃度C₁、處理溫度T₁和處理時間P₁與步驟(2)的酸的濃度C₂、處理溫度T₂和處理時間P₂之間滿足以下關係：500≦C₁×P₁×(T₁+273.15)≦4,500；和350≦C₂×P₂×(T₂+273.15)≦3,000；再進一步優選：650≦C₁×P₁×(T₁+273.15)≦3,800；和450≦C₂×P₂×(T₂+273.15)≦2,500；更進一步優選：850≦C₁×P₁×(T₁+273.15)≦3,200；和550≦C₂×P₂×(T₂+273.15)≦2,200。 It is further preferred that the acid concentration C ₁ , the treatment temperature T ₁ and the treatment time P ₁ of the step (1) and the acid concentration C _{2 of the} step (2), the treatment temperature T ₂ and the treatment time P ₂ satisfy the following Relationship: 500 ≦C ₁ ×P ₁ ×(T ₁ +273.15)≦4,500; and 350≦C ₂ ×P ₂ ×(T ₂ +273.15)≦3,000; still more preferably: 650≦C ₁ ×P ₁ ×( T ₁ +273.15)≦3,800; and 450≦C ₂ ×P ₂ ×(T ₂ +273.15)≦2,500; still more preferably: 850≦C ₁ ×P ₁ ×(T ₁ +273.15)≦3,200; and 550≦ C ₂ × P ₂ × (T ₂ + 273.15) ≦ 2,200.

在本發明中，所使用的術語「高純水」是指在25℃的電阻率優選不低於15百萬歐姆×公分(1.5×10⁷Ω×cm)，更優選不低於17.5百萬歐姆×公分的水。 In the present invention, as the term "high-purity water" refers to the resistivity of preferably 25 deg.] C is not less than 15 million ohms × cm ^{(1.5 × 10 7 Ω × cm} ), more preferably not less than 17.5 million ohms × The water of centimeters.

在用高純水洗滌晶圓的步驟(3)、(5)和(7)中，各步驟優選在較低溫度進行，例如在不高於30℃的溫度(例如3-30℃)，優選在不高於25℃(例如5-25℃)的溫度，更優選在8-20℃的溫度實施。洗滌時間通常為10-100秒，優選12-80秒，更優選15-60秒。 In the steps (3), (5) and (7) of washing the wafer with high-purity water, the respective steps are preferably carried out at a lower temperature, for example, at a temperature not higher than 30 ° C (for example, 3 to 30 ° C), preferably at no A temperature higher than 25 ° C (for example, 5 to 25 ° C) is more preferably carried out at a temperature of 8 to 20 ° C. The washing time is usually from 10 to 100 seconds, preferably from 12 to 80 seconds, more preferably from 15 to 60 seconds.

在本發明方法的步驟(4)(用一種有機酸溶液處理晶圓)中，所用的有機酸可以為常用的一種有機多元酸。所述酸包括，但不限於，檸檬酸、酒石酸、馬來酸、富馬酸、蘋果酸、葡萄糖酸、葡萄庚糖酸、C3-C12(即3-12個碳原子)的多元酸，優選C3-C10的二元酸等，例如丙二酸、丁二酸、戊二酸、己二酸、庚二酸、壬二酸、癸二酸等，優選檸檬酸。所述有機酸的濃度C₄通常為1-10重量%，優選2-8重量%，更優選3-6重量%。用有機酸處理時的溫度T₄通常為10-30℃，優選15-25℃。該處理步驟中的溫度可以變化。該步驟的處理時間P₄通常為15-35秒，優選20-33秒。所述處理包括，但不限於，沖洗和浸入等，優選浸入處理。 In the step (4) of the method of the present invention (treatment of the wafer with an organic acid solution), the organic acid used may be a commonly used organic polybasic acid. The acid includes, but is not limited to, a polybasic acid of citric acid, tartaric acid, maleic acid, fumaric acid, malic acid, gluconic acid, glucoheptonic acid, C3-C12 (ie, 3-12 carbon atoms), preferably A dibasic acid or the like of C3-C10, for example, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, sebacic acid, sebacic acid or the like, preferably citric acid. The concentration C _{4 of} the organic acid is usually from 1 to 10% by weight, preferably from 2 to 8% by weight, more preferably from 3 to 6% by weight. The temperature T ₄ when treated with an organic acid is usually 10 to 30 ° C, preferably 15 to 25 ° C. The temperature in this processing step can vary. The treatment time P _{4 of} this step is usually from 15 to 35 seconds, preferably from 20 to 33 seconds. The treatment includes, but is not limited to, rinsing and immersion, etc., preferably immersion treatment.

在本發明一個特別優選的實施方案中，步驟(1)、步驟(2)中酸的濃度、處理溫度、處理時間與步驟(4)中酸的濃度C₄、處理溫度T₄和處理時間P₄滿足以下關係：1/10[C₂×P₂×(T₂+273.15)+C₁×P₁×(T₁+273.15)]≦C₄×P₄×(T₄+273.15)≦1/2[C₂×P₂×(T₂+273.15)+C₁×P₁×(T₁+273.15)]，以上各式中，濃度單位為重量百分比濃度，處理溫度為攝氏度，處理時間為秒。 In a particularly the present invention, preferred embodiments, step (1), Step (2) the concentration of the acid, the treatment temperature, the treatment time in step (4) the concentration of C in the acid _4, the treatment temperature T ₄ and the processing time P ₄ satisfies the following relationship: 1/10 [C ₂ × P ₂ × (T ₂ + 273.15) + C ₁ × P ₁ × (T ₁ + 273.15)] ≦ C ₄ × P ₄ × (T ₄ + 273.15) ≦ 1 /2[C ₂ ×P ₂ ×(T ₂ +273.15)+C ₁ ×P ₁ ×(T ₁ +273.15)], in the above formulas, the concentration unit is the weight percentage concentration, the treatment temperature is Celsius, and the treatment time is second.

進一步優選的是，步驟(4)中酸的濃度C₄、處理溫度T₄和處理時間P₄滿足以下關係：100≦C₄×P₄×(T₄+273.15)≦1,200。 Further preferably, the step (4) the concentration of acid in ₄ C, the treatment temperature and treatment time T ₄ P ₄ satisfy the following _{_{relation: 100 ≦ C 4 × P 4}} × (T 4 +273.15) ≦ 1,200.

更進一步優選的是，200≦C₄×P₄×(T₄+273.15)≦900。 Still more preferably, 200 ≦ C ₄ × P ₄ × (T ₄ + 273.15) ≦ 900.

在本發明方法的步驟(6)(用一種NH₄OH-H₂O₂溶液處理晶圓)中，採用NH₄OH-H₂O₂水溶液，按重量百分比計算，所述NH₄OH-H₂O₂水溶液中，NH₄OH、H₂O₂的濃度通常分別為5-25%NH₄OH和3-15% H₂O₂，優選為10-22% NH₄OH和5-12% H₂O₂。處理過程有利地在10-40℃下進行，優選在15-30℃的溫度進行。該處理步驟中的溫度可以變化。該步驟的處理時間通常為2-15秒，優選3-12秒，更優選4-10秒。所述處理包括，但不限於，沖洗或浸入等，優選浸入處理。 In the step (6) of the method of the invention (treatment of the wafer with a solution of NH ₄ OH-H ₂ O ₂ ), the NH ₄ OH-H ₂ O ₂ aqueous solution is used, and the NH ₄ OH-H is calculated by weight percentage. ₂ O ₂ aqueous solution, NH ₄ OH, H ₂ O ₂ concentrations are typically 5-25% NH ₄ OH, and 3-15% H _₂ O _{_2,} preferably 10-22% NH ₄ OH and 5-12% H ₂ O ₂ . The treatment is advantageously carried out at 10-40 ° C, preferably at a temperature of 15-30 ° C. The temperature in this processing step can vary. The treatment time for this step is usually from 2 to 15 seconds, preferably from 3 to 12 seconds, more preferably from 4 to 10 seconds. The treatment includes, but is not limited to, rinsing or immersion, etc., preferably immersion treatment.

在本發明的一個特別優選的實施方案中，步驟(6)中氨水的濃度C₆、步驟(6)的處理溫度T₆和處理時間P₆滿足以下關係：50≦C₆×P₆×(T₆+273.15)≦1,000優選的是，80≦C₆×P₆×(T₆+273.15)≦800進一步優選的是，100≦C₆×P₆×(T₆+273.15)≦500 In a particularly preferred embodiment of the present invention, the concentration C ₆ of the aqueous ammonia, the treatment temperature T _{6 of the} step (6), and the treatment time P _{6 in the} step (6) satisfy the following relationship: 50 ≦ C ₆ × P ₆ × ( T ₆ +273.15) ≦ 1,000 is _{_{preferably, 80 ≦ C 6 × P 6}} × (T 6 +273.15) ≦ 800 further _{_{preferably, 100 ≦ C 6 × P 6}} × (T 6 +273.15) ≦ 500

上述各式中，濃度單位為重量百分比濃度，處理溫度為攝氏度，處理時間為秒。 In the above formulas, the concentration unit is the weight percentage concentration, and the treatment temperature In degrees Celsius, the processing time is seconds.

在本發明方法的步驟(6)中，按重量百分比計算，NH₄OH與H₂O₂的比例優選為0.5-7.5：1，優選為1-5：1。 In the step (6) of the process of the invention, the ratio of NH ₄ OH to H ₂ O ₂ is preferably from 0.5 to 7.5:1, preferably from 1 to 5:1, by weight percent.

在本發明方法的步驟(8)中，可以選擇在空氣或惰性氣氛(氮氣等)中乾燥晶圓，或選擇真空乾燥，乾燥溫度優選20-120℃，優選25-90℃；乾燥時間優選1-20分鐘。 In the step (8) of the method of the present invention, the wafer may be selected to be dried in air or an inert atmosphere (nitrogen or the like), or vacuum drying may be selected, and the drying temperature is preferably 20-120 ° C, preferably 25-90 ° C; the drying time is preferably 1 -20 minutes.

本發明方法優選地適於清洗III-V族化合物半導體晶圓，例如直徑為2.50-15.0公分的晶圓，例如直徑5.0公分、7.5公分、10.0公分、12.5公分和15.0公分的III-V族化合物半導體晶圓，尤其是磷化銦半導體晶圓。所得的III-V族化合物半導體晶圓，每平方公分晶圓表面面積大於0.11 μm²的顆粒≦0.5顆(按統計數除以晶圓表面積計)，優選≦0.3顆；晶圓表面的金屬殘留Cu≦10×10¹⁰原子/cm²且Zn≦10×10¹⁰原子/cm²，優選金屬殘留Cu≦7×10¹⁰原子/cm²且Zn≦8×10¹⁰原子/cm²，更優選金屬殘留Cu≦2×10¹⁰原子/cm²且Zn≦3×10¹⁰原子/cm²；表面平均白霧值≦1.0 ppm，優選表面平均白霧值≦0.8 ppm，更優選≦0.7 ppm；其表面微觀粗糙度Ra0.5 nm(用AFM(原子力顯微鏡)測試)，優選Ra0.3 nm。通常，晶圓單面拋光；如果要求兩面拋光，則上述參數為兩面的平均值。 The method of the present invention is preferably suitable for cleaning III-V compound semiconductor wafers, such as wafers having a diameter of 2.50-15.0 cm, such as III-V compounds having a diameter of 5.0 cm, 7.5 cm, 10.0 cm, 12.5 cm, and 15.0 cm. Semiconductor wafers, especially indium phosphide semiconductor wafers. The obtained III-V compound semiconductor wafer has 0.5 particles per square centimeter of wafer surface area greater than 0.11 μm ² (calculated by dividing the surface area of the wafer by statistic), preferably ≦ 0.3; metal residue on the surface of the wafer Cu ≦ 10 × 10 ¹⁰ atoms/cm ² and Zn ≦ 10 × 10 ¹⁰ atoms/cm ² , preferably metal residual Cu ≦ 7 × 10 ¹⁰ atoms/cm ² and Zn ≦ 8 × 10 ¹⁰ atoms/cm ² , more preferably metal Residual Cu ≦ 2 × 10 ¹⁰ atoms / cm ² and Zn ≦ 3 × 10 ¹⁰ atoms / cm ² ; surface average white fog value ≦ 1.0 ppm, preferably surface average white fog value ≦ 0.8 ppm, more preferably ≦ 0.7 ppm; Micro roughness Ra 0.5 nm (tested by AFM (atomic force microscope)), preferably Ra 0.3 nm. Typically, the wafer is polished on one side; if two sides are required to be polished, the above parameters are the average of the two sides.

因此，本發明還提供一種III-V族化合物半導體晶圓，其特徵在於，每平方公分晶圓表面面積大於0.11 μm²的顆粒≦0.5顆(按統計數除以晶圓表面積計)，優選≦0.3顆；晶圓表面的金屬殘留Cu≦10×10¹⁰原子/cm²且Zn≦ 10×10¹⁰原子/cm²，優選金屬殘留Cu≦7×10¹⁰原子/cm²且Zn≦8×10¹⁰原子/cm²，更優選金屬殘留Cu≦2×10¹⁰原子/cm²且Zn≦3×10¹⁰原子/cm²；表面平均白霧值≦1.0 ppm，優選表面平均白霧值≦0.8 ppm，更優選≦0.7 ppm；其表面微觀粗糙度Ra0.5 nm(用AFM(原子力顯微鏡)測試)，優選Ra0.3 nm。通常，晶圓單面拋光；如果要求兩面拋光，則上述參數為兩面的平均值。所述III-V族化合物半導體晶圓例如直徑為2.50-15.0公分的晶圓，例如直徑5.0公分、7.5公分、10.0公分、12.5公分和15.0公分的III-V族化合物半導體晶圓，尤其是磷化銦半導體晶圓。 Therefore, the present invention also provides a III-V compound semiconductor wafer, characterized in that: 0.5 particles per square centimeter of wafer surface area greater than 0.11 μm ² (calculated by dividing the surface area of the wafer), preferably ≦ 0.3 particles; metal residue on the surface of the wafer Cu ≦ 10 × 10 ¹⁰ atoms / cm ² and Zn ≦ 10 × 10 ¹⁰ atoms / cm ² , preferably metal residual Cu ≦ 7 × 10 ¹⁰ atoms / cm ² and Zn ≦ 8 × 10 ¹⁰ atoms/cm ² , more preferably metal residual Cu ≦ 2 × 10 ¹⁰ atoms/cm ² and Zn ≦ 3 × 10 ¹⁰ atoms/cm ² ; surface average white fog value ≦ 1.0 ppm, preferably surface average white fog value ≦ 0.8 ppm More preferably ≦0.7 ppm; its surface micro-roughness Ra 0.5 nm (tested by AFM (atomic force microscope)), preferably Ra 0.3 nm. Typically, the wafer is polished on one side; if two sides are required to be polished, the above parameters are the average of the two sides. The III-V compound semiconductor wafer, for example, a wafer having a diameter of 2.50-15.0 cm, such as a III-V compound semiconductor wafer having a diameter of 5.0 cm, 7.5 cm, 10.0 cm, 12.5 cm, and 15.0 cm, especially phosphorus Indium semiconductor wafers.

在本發明中，如無另外說明，則所有的百分比或份數均按重量計。如無另外說明，則所有濃度均基於所述物質的純物質計算。 In the present invention, all percentages or parts are by weight unless otherwise stated. All concentrations are calculated based on the pure substance of the substance, unless otherwise stated.

實施例：儀器和裝置：濕法清洗台(包含浸泡晶圓的槽和水洗槽)；晶圓旋轉乾燥機(美國Semitool公司101型SRD)。 EXAMPLES: Instruments and devices: wet cleaning stations (including tanks and washing tanks for soaking wafers); wafer rotary dryers (Semitool Model SRD, USA).

晶圓品質檢測儀器：Yamada強光燈(光強大於100,000Lux)；晶圓表面分析儀(美國KLA-TENCOR公司6220型)；原子力顯微鏡(AFM)(美國Digital Instrument公司 NanoScope IIIa型)(垂直解析度0.03 nm，分析區域5 μm×5 μm)；用TXRF(反射X射線螢光分析儀；TREX 610型，OSAKA Japan Technos公司)測試晶圓表面元素。 Wafer quality inspection equipment: Yamada glare (light is stronger than 100,000 Lux); wafer surface analyzer (KLA-TENCOR company 6220); atomic force microscope (AFM) (Digital Instrument, USA) NanoScope Type IIIa) (Vertical resolution 0.03 nm, analysis area 5 μm × 5 μm); Wafer surface elements were tested with TXRF (Reflective X-Ray Fluorescence Analyzer; TREX Model 610, OSAKA Japan Technos).

實驗晶圓：如無另外說明，則均採用直徑5.08公分(2英吋)的、其中一面經過精細鏡面拋光的磷化銦晶圓，厚度為350 μm，拋光面表面微觀粗糙度Ra=0.3 nm。所有檢測均針對拋光面(對非磷化銦晶圓也是如此)。 Experimental Wafer: Unless otherwise stated, an indium phosphide wafer with a diameter of 5.08 cm (2 inches), one of which was finely mirror polished, with a thickness of 350 μm, and a micro-roughness of the polished surface Ra = 0.3 nm . All tests are for polished surfaces (as for non-indium phosphide wafers).

對比例1 Comparative example 1

用以下步驟清洗磷化銦晶圓：(1)將待洗晶圓浸入93重量%的濃硫酸中於65℃處理3秒；(2)將上述晶圓取出然後浸入98重量%濃硫酸中於25℃處理3秒；(3)然後於25℃下，將晶圓放入沖洗槽中，用電阻率大於17.5百萬歐姆的快速高純水沖洗晶圓表面55秒；(4)將沖洗過的晶圓浸入NH₄OH-H₂O₂溶液(H₂O₂：NH₄OH：H₂O的重量比為1：2：7)中於25℃處理7秒；(5)然後於25℃下，將晶圓放入沖洗槽中，用電阻率大於17.5百萬歐姆的高純水沖洗晶圓表面30秒； (6)將沖洗後的晶圓放入晶圓旋轉乾燥機中用熱氮氣(70℃)乾燥15分鐘。 The indium phosphide wafer is cleaned by the following steps: (1) immersing the wafer to be washed in 93% by weight of concentrated sulfuric acid at 65 ° C for 3 seconds; (2) taking the above wafer and immersing it in 98% by weight of concentrated sulfuric acid Processing at 25 ° C for 3 seconds; (3) then placing the wafer into the rinse tank at 25 ° C, rinsing the wafer surface with fast high-purity water with a resistivity greater than 17.5 million ohms for 55 seconds; (4) rinsing the crystal The circle was immersed in a NH ₄ OH-H ₂ O ₂ solution (H ₂ O ₂ :NH ₄ OH:H ₂ O in a weight ratio of 1:2:7) at 25 ° C for 7 seconds; (5) then at 25 ° C The wafer is placed in a rinse tank, and the surface of the wafer is rinsed with high-purity water having a resistivity of more than 17.5 million ohms for 30 seconds; (6) The rinsed wafer is placed in a wafer rotary dryer with hot nitrogen (70 ° C) ) Dry for 15 minutes.

乾燥後的晶圓用強光燈、KLA-TENCOR 6220、原子力顯微鏡燈檢查表面。 The dried wafer was inspected with a strong light, KLA-TENCOR 6220, and atomic force microscope lamp.

用強光燈檢查晶圓表面，無可見顆粒、但是有白霧。用美國KLA-TENCOR 6220型檢查，面積大於0.11 μm²的顆粒18顆(0.89顆/cm²)，白霧值(Haze值)=1.3 ppm。用TXRF測量金屬含量，Cu=20x10¹¹原子/cm²，Zn=23x10¹¹原子/cm²。 The surface of the wafer was inspected with a strong light, with no visible particles but white fog. For the inspection of KLA-TENCOR 6220 type in the United States, 18 particles (0.89 particles/cm ² ) having an area larger than 0.11 μm ^{2 and} a haze value (1.3 mg) were used. Metal content measured by TXRF, Cu = 20x10 ¹¹ atoms / cm ^2, Zn = 23x10 ¹¹ atoms / cm ^2.

對比例2 Comparative example 2

用以下步驟清洗磷化銦晶圓：(1)將待洗晶圓浸入90重量%的濃硫酸中於65℃處理3秒；(2)將上述晶圓取出然後浸入95重量%濃硫酸中於25℃處理2秒；(3)然後於25℃下，將晶圓放入沖洗槽中，用電阻率大於17.5百萬歐姆的快速高純水沖洗晶圓表面55秒；(4)用4重量%稀硫酸於25℃處理晶圓30秒；(5)於25℃下，將晶圓放入沖洗槽中，用電阻率大於17.5百萬歐姆的快速高純水沖洗晶圓表面55秒；(6)將沖洗過的晶圓浸入NH₄OH-H₂O₂溶液(H₂O₂：NH₄OH：H₂O的重量比為1：2：7)中於25℃處理5秒； (7)然後於25℃下，將晶圓放入沖洗槽中，用電阻率大於17.5百萬歐姆的高純水沖洗晶圓表面30秒；(8)將沖洗後的晶圓放入晶圓旋轉乾燥機中用熱氮氣(70℃)乾燥15分鐘。 The indium phosphide wafer is cleaned by the following steps: (1) immersing the wafer to be washed in 90% by weight of concentrated sulfuric acid at 65 ° C for 3 seconds; (2) taking the above wafer and immersing it in 95% by weight of concentrated sulfuric acid 25 ° C for 2 seconds; (3) then at 25 ° C, the wafer is placed in the rinse tank, the surface of the wafer is rinsed with fast high purity water with a resistivity greater than 17.5 million ohms for 55 seconds; (4) diluted with 4 wt% Sulfuric acid is treated at 25 ° C for 30 seconds; (5) at 25 ° C, the wafer is placed in the rinse tank, and the wafer surface is rinsed with fast high-purity water with a resistivity greater than 17.5 million ohms for 55 seconds; (6) will be rinsed The wafer is immersed in a NH ₄ OH-H ₂ O ₂ solution (H ₂ O ₂ :NH ₄ OH:H ₂ O in a weight ratio of 1:2:7) at 25 ° C for 5 seconds; (7) then At 25 ° C, the wafer was placed in a rinse tank, and the surface of the wafer was rinsed with high-purity water having a resistivity of more than 17.5 million ohms for 30 seconds; (8) the rinsed wafer was placed in a wafer rotary dryer with hot nitrogen. (70 ° C) drying for 15 minutes.

用強光燈檢查晶圓表面，無可見顆粒、無白霧。用美國KLA-TENCOR 6220型檢查，面積大於0.11 μm²的顆粒=20顆(=0.99顆/cm²)，白霧值(Haze值)=1.5 ppm。用TXRF測量金屬含量，Cu=21x10¹⁰原子/cm²，Zn=23x10¹⁰原子/cm²。 The surface of the wafer was inspected with a strong light, with no visible particles or white fog. With the US KLA-TENCOR 6220 type, the particles with an area larger than 0.11 μm ² = 20 particles (= 0.99 particles/cm ² ), and the white fog value (Haze value) = 1.5 ppm. The metal content was measured by TXRF, Cu = 21 x ^{10 10} atoms/cm ² , and Zn = 23 x ^{10 10} atoms/cm ² .

對比例3 Comparative example 3

用以下步驟清洗磷化銦晶圓：(1)將待洗晶圓浸入95重量%的濃硫酸中於65℃處理4秒；(2)將上述晶圓取出然後浸入95重量%濃硫酸中於25℃處理10秒；(3)然後於25℃下，將晶圓放入沖洗槽中，用電阻率大於17.5百萬歐姆的快速高純水沖洗晶圓表面55秒；(4)將沖洗過的晶圓浸入6重量%的硝酸溶液中於25℃處理30秒；(5)然後將晶圓放入沖洗槽中，於25℃下，用電阻率大於17.5百萬歐姆的高純水沖洗晶圓表面20秒； (6)將沖洗過的晶圓浸入NH₄OH-H₂O₂溶液(H₂O₂：NH₄OH：H₂O的重量比為1：2：7)中於22℃處理6秒；(7)然後於25℃下，將晶圓放入沖洗槽中，用電阻率大於17.5百萬歐姆的高純水沖洗晶圓表面30秒；(8)將沖洗後的晶圓放入晶圓旋轉乾燥機中用熱氮氣(70℃)乾燥15分鐘。 The indium phosphide wafer is cleaned by the following steps: (1) immersing the wafer to be washed in 95% by weight of concentrated sulfuric acid at 65 ° C for 4 seconds; (2) taking the above wafer and immersing it in 95% by weight of concentrated sulfuric acid Processing at 25 ° C for 10 seconds; (3) then placing the wafer into the rinse tank at 25 ° C, rinsing the wafer surface with fast high purity water with a resistivity greater than 17.5 million ohms for 55 seconds; (4) rinsing the crystal The circle was immersed in a 6 wt% nitric acid solution at 25 ° C for 30 seconds; (5) the wafer was then placed in a rinse tank, and the wafer surface was rinsed with high-purity water having a resistivity greater than 17.5 million ohms at 25 ° C for 20 seconds. (6) The immersed wafer is immersed in a NH ₄ OH-H ₂ O ₂ solution (H ₂ O ₂ :NH ₄ OH:H ₂ O weight ratio 1:2:7) at 22 ° C for 6 seconds. (7) Then, at 25 ° C, the wafer is placed in a rinse tank, and the wafer surface is rinsed with high-purity water having a resistivity of more than 17.5 million ohms for 30 seconds; (8) the rinsed wafer is placed in the wafer rotation. Dry in a dryer with hot nitrogen (70 ° C) for 15 minutes.

乾燥後的晶圓用強光燈、KLA-TENCOR 6220型、原子力顯微鏡燈檢查表面。 The dried wafer was inspected with a strong light, KLA-TENCOR Model 6220, and an atomic force microscope lamp.

用強光燈檢查晶圓表面，無可見顆粒、無白霧。用KLA-TENCOR 6220型檢查，面積大於0.11 μm²的顆粒=22顆(1.09顆/cm²)，白霧值(Haze值)=1.2 ppm。用TXRF測量金屬含量，Cu=22x10¹⁰原子/cm²，Zn=21x10¹⁰原子/cm²。 The surface of the wafer was inspected with a strong light, with no visible particles or white fog. With KLA-TENCOR 6220 type, particles with an area larger than 0.11 μm ² = 22 particles (1.09 particles/cm ² ), and a haze value (Haze value) = 1.2 ppm. The metal content was measured by TXRF, Cu = 22 x ^{10 10} atoms/cm ² and Zn = 21 x ^{10 10} atoms/cm ² .

實施例1 Example 1

用以下步驟清洗直徑5.08公分(2英吋)的經過精細鏡面拋光的砷化鎵晶圓，厚度為350 μm，表面微觀粗糙度Ra=0.3 nm：(1)將待洗晶圓浸入92重量%的濃硫酸中於65℃處理4秒；(2)將上述晶圓取出然後浸入98重量%濃硫酸中於25℃處理2秒；(3)然後於20℃，將晶圓放入沖洗槽中，用電阻率大於17.5百萬歐姆的快速高純水沖洗晶圓表面55秒；(4)將沖洗過的晶圓浸入8重量%的檸檬酸溶液中於25℃處理30秒；(5)然後將晶圓放入沖洗槽中，於20℃，用電阻率大於17.5百萬歐姆的高純水沖洗晶圓表面20秒；(6)將沖洗過的晶圓浸入NH₄OH-H₂O₂溶液(H₂O₂：NH₄OH：H₂O的重量比為1：2：7)中於25℃處理5秒；(7)然後於20℃，將晶圓放入沖洗槽中，用電阻率大於17.5百萬歐姆的高純水沖洗晶圓表面30秒；(8)將沖洗後的晶圓放入晶圓旋轉乾燥機中用熱氮氣(70℃)乾燥15分鐘。 Use the following procedure to clean a 5.08 cm (2 in.) diameter finely mirrored GaAs wafer with a thickness of 350 μm and a surface micro-roughness Ra = 0.3 nm: (1) Immerse the wafer to be washed at 92% by weight. The concentrated sulfuric acid was treated at 65 ° C for 4 seconds; (2) the above wafer was taken out and then immersed in 98% by weight of concentrated sulfuric acid at 25 ° C for 2 seconds; (3) then the wafer was placed in the rinse tank at 20 ° C Rinse the wafer surface with fast high purity water with a resistivity greater than 17.5 million ohms for 55 seconds; (4) immerse the rinsed wafer in an 8 wt% citric acid solution for 30 seconds at 25 ° C; (5) then crystallize The circle was placed in a rinse tank, and the surface of the wafer was rinsed with high-purity water having a resistivity of more than 17.5 million ohms at 20 ° C for 20 seconds; (6) the rinsed wafer was immersed in a NH ₄ OH-H ₂ O ₂ solution (H ₂ O ₂ :NH ₄ OH:H ₂ O in a weight ratio of 1:2:7) at 25 ° C for 5 seconds; (7) then at 20 ° C, the wafer is placed in the rinse tank, with a resistivity greater than 17.5 Million ohms of high purity water was used to rinse the wafer surface for 30 seconds; (8) The rinsed wafer was placed in a wafer rotary dryer and dried with hot nitrogen (70 ° C) for 15 minutes.

用強光燈檢查晶圓表面，無可見顆粒、無白霧。用KLA-TENCOR 6220型檢查，面積大於0.11 μm²的顆粒6顆(0.30顆/cm²)，白霧值(Haze值)=0.7 ppm。用TXRF測量金屬含量，Cu=4x10¹⁰原子/cm²，Zn=3x10¹⁰原子/cm²。 The surface of the wafer was inspected with a strong light, with no visible particles or white fog. With KLA-TENCOR 6220 type, 6 particles (0.30 particles/cm ² ) having an area larger than 0.11 μm ^{2 and} a haze value (0.7 mg) were used. Metal content measured by TXRF, Cu = 4x10 ¹⁰ atoms / cm ^2, Zn = 3x10 ¹⁰ atoms / cm ^2.

實施例2 Example 2

用以下步驟清洗磷化銦晶圓：(1)將待洗晶圓浸入68重量%的濃硝酸中於51℃處理7秒；(2)將上述晶圓取出然後浸入68重量%濃硝酸中於23 ℃處理4秒；(3)然後於25℃下，將晶圓放入沖洗槽中，用電阻率大於17.5百萬歐姆的快速高純水沖洗晶圓表面55秒；(4)將沖洗過的晶圓浸入3重量%的庚二酸溶液中於20℃處理30秒；(5)然後將晶圓放入沖洗槽中，於25℃下，用電阻率大於17.5百萬歐姆的高純水沖洗晶圓表面20秒；(6)將沖洗過的晶圓浸入NH₄OH-H₂O₂溶液(H₂O₂：NH₄OH：H₂O的重量比為1：1：8)中於20℃處理6秒；(7)然後於25℃下，將晶圓放入沖洗槽中，用電阻率大於17.5百萬歐姆的高純水沖洗晶圓表面30秒；(8)將沖洗後的晶圓放入晶圓旋轉乾燥機中用熱氮氣(70℃)乾燥15分鐘。 The indium phosphide wafer is cleaned by the following steps: (1) immersing the wafer to be washed in 68% by weight of concentrated nitric acid at 51 ° C for 7 seconds; (2) taking out the wafer and immersing it in 68% by weight of concentrated nitric acid Processing at 23 °C for 4 seconds; (3) then placing the wafer into the rinse tank at 25 ° C, rinsing the wafer surface with fast high-purity water with a resistivity greater than 17.5 million ohms for 55 seconds; (4) rinsing the crystal The circle is immersed in a 3 wt% pimelic acid solution at 20 ° C for 30 seconds; (5) the wafer is then placed in a rinse tank, and the wafer surface is rinsed with high purity water having a resistivity greater than 17.5 million ohms at 25 ° C. 20 seconds; (6) immersing the rinsed wafer in a NH ₄ OH-H ₂ O ₂ solution (H ₂ O ₂ :NH ₄ OH:H ₂ O weight ratio of 1:1:8) at 20 ° C 6 seconds; (7) then at 25 ° C, the wafer is placed in the rinse tank, the surface of the wafer is rinsed with high purity water with a resistivity greater than 17.5 million ohms for 30 seconds; (8) the rinsed wafer is placed in the crystal Dry in a rotary spin dryer with hot nitrogen (70 ° C) for 15 minutes.

用強光燈檢查晶圓表面，無可見顆粒、無白霧。用KLA-TENCOR 6220型檢查，面積大於0.11 μm²的顆粒8顆(0.39顆/cm²)，白霧值(Haze值)=0.75 ppm。用TXRF測量金屬含量，Cu=4x10¹⁰原子/cm²，Zn=4x10¹⁰原子/cm²。 The surface of the wafer was inspected with a strong light, with no visible particles or white fog. With KLA-TENCOR 6220 type, 8 particles (0.39 cells/cm ² ) having an area larger than 0.11 μm ^{2 and} a haze value (Haze value) = 0.75 ppm were examined. The metal content was measured by TXRF, Cu = 4 x ^{10 10} atoms/cm ² and Zn = 4 x ^{10 10} atoms/cm ² .

實施例3 Example 3

用以下步驟清洗磷化銦晶圓：(1)將待洗晶圓浸入90重量%的濃硫酸中於70℃處理 7秒；(2)將上述晶圓取出然後浸入93重量%濃硫酸中於22℃處理6秒；(3)然後於25℃下，將晶圓放入沖洗槽中，用電阻率大於17.5百萬歐姆的快速高純水沖洗晶圓表面55秒；(4)將沖洗過的晶圓浸入3重量%的檸檬酸溶液中於22℃處理30秒；(5)然後將晶圓放入沖洗槽中，於25℃下，用電阻率大於17.5百萬歐姆的高純水沖洗晶圓表面20秒；(6)將沖洗過的晶圓浸入NH₄OH-H₂O₂溶液(H₂O₂：NH₄OH：H₂O的重量比為0.7：1.8：7.5)中於30℃處理8秒；(7)然後於25℃下，將晶圓放入沖洗槽中，用電阻率大於17.5百萬歐姆的高純水沖洗晶圓表面30秒；(8)將沖洗後的晶圓放入晶圓旋轉乾燥機中用熱氮氣(70℃)乾燥15分鐘。 The indium phosphide wafer is cleaned by the following steps: (1) immersing the wafer to be washed in 90% by weight of concentrated sulfuric acid at 70 ° C for 7 seconds; (2) taking the above wafer and immersing it in 93% by weight of concentrated sulfuric acid Processing at 22 ° C for 6 seconds; (3) then placing the wafer into the rinse tank at 25 ° C, rinsing the wafer surface with fast high-purity water with a resistivity greater than 17.5 million ohms for 55 seconds; (4) rinsing the crystal The circle was immersed in a 3% by weight citric acid solution at 22 ° C for 30 seconds; (5) the wafer was then placed in a rinse tank, and the wafer surface was rinsed with high purity water having a resistivity greater than 17.5 million ohms at 25 ° C. (6) The immersed wafer is immersed in a NH ₄ OH-H ₂ O ₂ solution (H ₂ O ₂ :NH ₄ OH:H ₂ O weight ratio of 0.7:1.8:7.5) at 30 ° C. Seconds; (7) then at 25 ° C, the wafer is placed in the rinse tank, the surface of the wafer is rinsed with high-purity water with a resistivity greater than 17.5 million ohms for 30 seconds; (8) the rinsed wafer is placed in the wafer Dry in a rotary drier with hot nitrogen (70 ° C) for 15 minutes.

用強光燈檢查晶圓表面，無可見顆粒、無白霧。用KLA-TENCOR 6220型檢查，面積大於0.11 μm²的顆粒10顆(0.49顆/cm²)，白霧值(Haze值)=0.85 ppm。用TXRF測量金屬含量，Cu=7x10¹⁰原子/cm²，Zn=8x10¹⁰原子/cm²。 The surface of the wafer was inspected with a strong light, with no visible particles or white fog. With KLA-TENCOR 6220 type, 10 particles (0.49 particles/cm ² ) having an area larger than 0.11 μm ^{2 and} a haze value (Haze value) = 0.85 ppm were examined. The metal content was measured by TXRF, Cu = 7 x ^{10 10} atoms/cm ² and Zn = 8 x ^{10 10} atoms/cm ² .

實施例4 Example 4

用以下步驟清洗磷化銦晶圓：(1)將待洗晶圓浸入92重量%的濃硫酸中於65℃處理4秒；(2)將上述晶圓取出然後浸入95重量%濃硫酸中於15℃處理4秒；(3)然後於25℃下，將晶圓放入沖洗槽中，用電阻率大於17.5百萬歐姆的快速高純水沖洗晶圓表面55秒；(4)將沖洗過的晶圓浸入3重量%的戊二酸溶液中於25℃處理30秒；(5)然後將晶圓放入沖洗槽中，於25℃下，用電阻率大於17.5百萬歐姆的高純水沖洗晶圓表面20秒；(6)將沖洗過的晶圓浸入NH₄OH-H₂O₂溶液(H₂O₂：NH₄OH：H₂O的重量比為1：1：8)中於18℃處理5秒；(7)然後於25℃下，將晶圓放入沖洗槽中，用電阻率大於17.5百萬歐姆的高純水沖洗晶圓表面30秒；(8)將沖洗後的晶圓放入晶圓旋轉乾燥機中用熱氮氣(70℃)乾燥15分鐘。 The indium phosphide wafer is cleaned by the following steps: (1) immersing the wafer to be washed in 92% by weight of concentrated sulfuric acid at 65 ° C for 4 seconds; (2) taking the above wafer and immersing it in 95% by weight of concentrated sulfuric acid Processing at 15 ° C for 4 seconds; (3) then placing the wafer into the rinse tank at 25 ° C, rinsing the wafer surface with fast high-purity water with a resistivity greater than 17.5 million ohms for 55 seconds; (4) rinsing the crystal The circle is immersed in a 3% by weight solution of glutaric acid at 25 ° C for 30 seconds; (5) the wafer is then placed in a rinse tank, and the wafer surface is rinsed with high-purity water having a resistivity greater than 17.5 million ohms at 25 ° C. 20 seconds; (6) immersing the rinsed wafer in an NH ₄ OH-H ₂ O ₂ solution (H ₂ O ₂ :NH ₄ OH:H ₂ O weight ratio 1:1:8) at 18 ° C 5 seconds; (7) then at 25 ° C, the wafer is placed in the rinse tank, the surface of the wafer is rinsed with high-purity water with a resistivity greater than 17.5 million ohms for 30 seconds; (8) the rinsed wafer is placed in the crystal Dry in a rotary spin dryer with hot nitrogen (70 ° C) for 15 minutes.

用強光燈檢查晶圓表面，無可見顆粒、無白霧。用KLA-TENCOR 6220型檢查，面積大於0.11 μm²的顆粒6顆(0.30顆/cm²)，白霧值(Haze值)=0.70 ppm。用TXRF 測量金屬含量，Cu=2x10¹⁰原子/cm²，Zn=3x10¹⁰原子/cm²。 The surface of the wafer was inspected with a strong light, with no visible particles or white fog. With KLA-TENCOR 6220 type, 6 particles (0.30 particles/cm ² ) having an area larger than 0.11 μm ^{2 and} a haze value (Haze value) = 0.70 ppm were examined. The metal content was measured by TXRF, Cu = 2 x ^{10 10} atoms/cm ² , and Zn = 3 x ^{10 10} atoms/cm ² .

實施例5 Example 5

用以下步驟清洗磷化銦晶圓：(1)將待洗晶圓浸入70重量%的濃硫酸中於62℃處理13秒；(2)將上述晶圓取出然後浸入70重量%濃硫酸中於30℃處理10秒；(3)然後於25℃下，將晶圓放入沖洗槽中，用電阻率大於17.5百萬歐姆的快速高純水沖洗晶圓表面55秒；(4)將沖洗過的晶圓浸入5重量%的己二酸溶液中於25℃處理20秒；(5)然後將晶圓放入沖洗槽中，於25℃下，用電阻率大於17.5百萬歐姆的高純水沖洗晶圓表面20秒；(6)將沖洗過的晶圓浸入NH₄OH-H₂O₂溶液(H₂O₂：NH₄OH：H₂O的重量比為1：1.5：7.5)中於15℃處理15秒；(7)然後於25℃下，將晶圓放入沖洗槽中，用電阻率大於17.5百萬歐姆的高純水沖洗晶圓表面30秒；(8)將沖洗後的晶圓放入晶圓旋轉乾燥機中用熱氮氣(70℃)乾燥15分鐘。 The indium phosphide wafer is cleaned by the following steps: (1) immersing the wafer to be washed in 70% by weight of concentrated sulfuric acid at 62 ° C for 13 seconds; (2) taking the above wafer and immersing it in 70% by weight of concentrated sulfuric acid Processing at 30 ° C for 10 seconds; (3) then placing the wafer into the rinse tank at 25 ° C, rinsing the wafer surface with fast high-purity water with a resistivity greater than 17.5 million ohms for 55 seconds; (4) rinsing the crystal The circle is immersed in a 5% by weight solution of adipic acid at 25 ° C for 20 seconds; (5) the wafer is then placed in a rinse tank, and the wafer surface is rinsed with high-purity water having a resistivity greater than 17.5 million ohms at 25 ° C. 20 seconds; (6) immersing the rinsed wafer in a NH ₄ OH-H ₂ O ₂ solution (H ₂ O ₂ : NH ₄ OH: H ₂ O weight ratio 1:1.5:7.5) at 15 ° C 15 seconds; (7) then at 25 ° C, the wafer is placed in the rinse tank, the surface of the wafer is rinsed with high purity water with a resistivity greater than 17.5 million ohms for 30 seconds; (8) the rinsed wafer is placed in the crystal Dry in a rotary spin dryer with hot nitrogen (70 ° C) for 15 minutes.

用強光燈檢查晶圓表面，無可見顆粒、無白霧。用 KLA-TENCOR 6220型檢查，面積大於0.11 μm²的顆粒10顆(0.49顆/cm²)，白霧值(Haze值)=0.97 ppm。用TXRF測量金屬含量，Cu=7x10¹⁰原子/cm²，Zn=9x10¹⁰原子/cm²。 The surface of the wafer was inspected with a strong light, with no visible particles or white fog. 6220 inspection KLA-TENCOR, an area greater than 0.11 μm ² is 10 particles (0.49 / cm ^2), the fog value (a Haze value) = 0.97 ppm. The metal content was measured by TXRF, Cu = 7 x ^{10 10} atoms/cm ² , and Zn = 9 x ^{10 10} atoms/cm ² .

上述實施例為本發明優選的實施方式，但本發明的實施方式並不受上述實施例的限制，其它的任何不背離本發明的精神實質與原理下所作的改變、替代、組合、簡化，均應為等效的置換方式，都包含在本發明的保護範圍之內。 The above embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above embodiments, and any other changes, substitutions, combinations, and simplifications made without departing from the spirit and principles of the present invention. Equivalent replacement means are included in the scope of protection of the present invention.

Claims

一種清洗III-V族化合物半導體晶圓的方法，包括以下步驟：(1)用一種濃酸於不低於50℃處理晶圓；(2)用一種濃酸於不高於30℃處理晶圓；(3)用高純水洗滌晶圓；(4)用一種有機酸溶液處理晶圓；(5)用高純水洗滌晶圓；(6)用一種NH₄OH-H₂O₂溶液處理晶圓；(7)用高純水洗滌晶圓；以及(8)乾燥所得晶圓。 A method for cleaning a III-V compound semiconductor wafer, comprising the steps of: (1) treating a wafer with a concentrated acid at not lower than 50 ° C; and (2) treating the wafer with a concentrated acid at not higher than 30 ° C (3) washing the wafer with high purity water; (4) treating the wafer with an organic acid solution; (5) washing the wafer with high purity water; (6) treating the wafer with a NH ₄ OH-H ₂ O ₂ solution; 7) washing the wafer with high purity water; and (8) drying the resulting wafer.

根據請求項1的方法，其特徵在於，步驟(1)使用的晶圓是已經完成機械化學拋光和化學精細拋光的晶圓，其表面微觀粗糙度Ra0.5nm。 The method according to claim 1, characterized in that the wafer used in the step (1) is a wafer which has been subjected to mechanical chemical polishing and chemical fine polishing, and has a surface micro-roughness Ra 0.5 nm.

根據請求項1的方法，其特徵在於，步驟(1)-(2)使用的所述濃酸為無機酸，其濃度為其相應溫度時的飽和濃度的60%以上。 The method according to claim 1, characterized in that the concentrated acid used in the steps (1) to (2) is a mineral acid whose concentration is 60% or more of the saturated concentration at the corresponding temperature.

根據請求項3的方法，其特徵在於，所述無機酸為硝酸或硫酸。 The method according to claim 3, characterized in that the inorganic acid is nitric acid or sulfuric acid.

根據請求項1的方法，其特徵在於，步驟(1)和(2)採用相同的酸進行處理。 The method according to claim 1, characterized in that the steps (1) and (2) are carried out using the same acid.

根據請求項1的方法，其特徵在於，步驟(1)的酸的濃度C₁、處理溫度T₁和處理時間P₁與步驟(2)的酸的濃度C₂、處理溫度T₂和處理時間P₂之間滿足以下關係：C₂×P₂×(T₂+273.15)≦C₁×P₁×(T₁+273.15)≦3×C₂×P₂×(T₂+273.15)，以上各式中，濃度單位為重量百分比濃度，處理溫度為攝氏度，處理時間為秒。 The method according to claim 1, characterized in that the acid concentration C _{1 of the} step (1), the treatment temperature T ₁ and the treatment time P ₁ and the acid concentration C _{2 of the} step (2), the treatment temperature T ₂ and the treatment time The following relationship is satisfied between P ₂ : C ₂ × P ₂ × (T ₂ + 273.15) ≦ C ₁ × P ₁ × (T ₁ + 273.15) ≦ 3 × C ₂ × P ₂ × (T ₂ + 273.15), or more In each formula, the concentration unit is a weight percentage concentration, the treatment temperature is Celsius, and the treatment time is seconds.

根據請求項1或6的方法，其特徵在於，步驟(1)的酸的濃度C₁、處理溫度T₁和處理時間P₁與步驟(2)的酸的濃度C₂、處理溫度T₂和處理時間P₂之間滿足以下關係：500≦C₁×P₁×(T₁+273.15)≦4,500；和350≦C₂×P₂×(T₂+273.15)≦3,000。 The method according to claim 1 or 6, characterized by the acid concentration C _{1 of the} step (1), the treatment temperature T ₁ and the treatment time P ₁ , the acid concentration C _{2 of the} step (2), the treatment temperature T ₂ and The following relationship is satisfied between the processing times P ₂ : 500 ≦ C ₁ × P ₁ × (T ₁ + 273.15) ≦ 4,500; and 350 ≦ C ₂ × P ₂ × (T ₂ + 273.15) ≦ 3,000.

根據請求項1的方法，其特徵在於，在步驟(4)中，所用的有機酸為檸檬酸、酒石酸、馬來酸、富馬酸、蘋果酸、葡萄糖酸、葡萄庚糖酸或C3-C12的多元酸。 The method according to claim 1, characterized in that, in the step (4), the organic acid used is citric acid, tartaric acid, maleic acid, fumaric acid, malic acid, gluconic acid, glucoheptonic acid or C3-C12. Polyacid.

根據請求項8的方法，其特徵在於，所述有機酸為C3-C10的二酸或檸檬酸。 The method according to claim 8, characterized in that the organic acid is a C3-C10 diacid or citric acid.

根據請求項1、8或9的方法，其特徵在於，所述有機酸濃度為1-10重量%。 The method according to claim 1, 8, or 9, characterized in that the organic acid concentration is from 1 to 10% by weight.

根據請求項1的方法，其特徵在於，步驟(1)、步驟(2)中酸的濃度、處理溫度、處理時間與步驟(4)中酸的濃度C₄、處理溫度T₄和處理時間P₄滿足以下關係：1/10[C₂×P₂×(T₂+273.15)+C₁×P₁×(T₁+273.15)]≦C₄×P₄×(T₄+273.15)≦1/2[C₂×P₂×(T₂+273.15)+C₁×P₁×(T₁+273.15)]，以上各式中，濃度單位為重量百分比濃度，處理溫度為攝氏度，處理時間為秒。 The method according to claim 1, characterized in that the concentration of the acid in the step (1), the step (2), the treatment temperature, the treatment time, the concentration of the acid C ₄ in the step (4), the treatment temperature T ₄ and the treatment time P ₄ satisfies the following relationship: 1/10 [C ₂ × P ₂ × (T ₂ + 273.15) + C ₁ × P ₁ × (T ₁ + 273.15)] ≦ C ₄ × P ₄ × (T ₄ + 273.15) ≦ 1 /2[C ₂ ×P ₂ ×(T ₂ +273.15)+C ₁ ×P ₁ ×(T ₁ +273.15)], in the above formulas, the concentration unit is the weight percentage concentration, the treatment temperature is Celsius, and the treatment time is second.

根據請求項1或11的方法，其特徵在於，步驟(4)中酸的濃度C₄、處理溫度T₄和處理時間P₄滿足以下關係：100≦C₄×P₄×(T₄+273.15)≦1,200。 The method according to claim 1 or 11, characterized in that the acid concentration C ₄ , the treatment temperature T ₄ and the treatment time P ₄ in the step (4) satisfy the following relationship: 100 ≦ C ₄ × P ₄ × (T ₄ + 273.15) ) ≦ 1,200.

根據請求項1的方法，其特徵在於，在步驟(6)中，採用NH₄OH-H₂O₂水溶液，氨水的濃度C₆、步驟(6)的處理溫度T₆和處理時間P₆滿足以下關係：50≦C₆×P₆×(T₆+273.15)≦1,000，上述各式中，濃度單位為重量百分比濃度，處理溫度為攝氏度，處理時間為秒。 The method according to claim 1, characterized in that in the step (6), the NH ₄ OH-H ₂ O ₂ aqueous solution is used, the ammonia concentration C ₆ , the treatment temperature T _{6 of the} step (6), and the treatment time P _{6 are} satisfied. The following relationship: 50 ≦C ₆ ×P ₆ ×(T ₆ +273.15) ≦1,000, in the above formulas, the concentration unit is a weight percentage concentration, the treatment temperature is Celsius, and the treatment time is seconds.

根據請求項13的方法，其特徵在於，在步驟(6)中，按重量百分比計算，NH₄OH與H₂O₂的比例優選為0.5-7.5：1。 The method according to claim 13, characterized in that, in the step (6), the ratio of NH ₄ OH to H ₂ O ₂ is preferably from 0.5 to 7.5:1 in terms of percentage by weight.

根據請求項1的方法，其特徵在於，所述III-V族化合物半導體晶圓是磷化銦半導體晶圓。 The method of claim 1, wherein the III-V compound semiconductor wafer is an indium phosphide semiconductor wafer.

一種根據請求項1的方法製備的III-V族化合物半導體晶圓，其特徵在於，每平方公分晶圓表面面積大於0.11μm²的顆粒≦0.5顆，晶圓表面的金屬殘留Cu≦10×10¹⁰原子/cm²且Zn≦10×10¹⁰原子/cm²，表面平均白霧值≦1.0ppm，其表面微觀粗糙度Ra0.5nm。 A III-V compound semiconductor wafer prepared according to the method of claim 1, characterized in that: 0.5 particles per square centimeter of wafer surface area greater than 0.11 μm ² , and metal residual Cu ≦ 10×10 on the wafer surface ¹⁰ atoms / cm ² and Zn ≦ ¹⁰ × 10 10 atoms / cm ^2, the average surface value of the fog ≦ 1.0ppm, the surface micro-roughness Ra 0.5 nm.

根據請求項16的III-V族化合物半導體晶圓，其特徵在於，每平方公分晶圓表面面積大於0.11μm²的顆粒≦0.3顆。 The III-V compound semiconductor wafer according to claim 16, characterized in that the number of particles per square centimeter of the wafer surface area is greater than 0.11 μm ² .

根據請求項16的III-V族化合物半導體晶圓，其特徵在於，晶圓表面的金屬殘留Cu≦7×10¹⁰原子/cm²。 The III-V compound semiconductor wafer according to claim 16, characterized in that the metal on the surface of the wafer has a residual Cu ≦ 7 × 10 ¹⁰ atoms/cm ² .

根據請求項16的III-V族化合物半導體晶圓，其特徵在於，晶圓表面的金屬殘留Cu≦2×10¹⁰原子/cm²。 The III-V compound semiconductor wafer according to claim 16, characterized in that the metal on the surface of the wafer has a residual Cu ≦ 2 × 10 ¹⁰ atoms/cm ² .

根據請求項16的III-V族化合物半導體晶圓，其特徵在於，晶圓表面的金屬殘留Zn≦8×10¹⁰原子/cm²。 The III-V compound semiconductor wafer according to claim 16, characterized in that the metal residue on the surface of the wafer is Zn ≦ 8 × 10 ¹⁰ atoms/cm ² .

根據請求項16的III-V族化合物半導體晶圓，其特徵在於，晶圓表面的金屬殘留Zn≦3×10¹⁰原子/cm²。 The III-V compound semiconductor wafer according to claim 16, characterized in that the metal residue on the surface of the wafer is Zn ≦ 3 × 10 ¹⁰ atoms/cm ² .

根據請求項16的III-V族化合物半導體晶圓，其特徵在於，表面平均白霧值≦0.8ppm。 The III-V compound semiconductor wafer according to claim 16, characterized in that the surface average white fog value is ppm0.8 ppm.

根據請求項16的III-V族化合物半導體晶圓，其特徵在於，表面平均白霧值≦0.7ppm。 The III-V compound semiconductor wafer according to claim 16, characterized in that the surface average white fog value is ppm0.7 ppm.

根據請求項16的III-V族化合物半導體晶圓，其特徵在於，表面微觀粗糙度Ra0.3nm。 The III-V compound semiconductor wafer according to claim 16, characterized in that the surface micro-roughness Ra 0.3 nm.

根據請求項16的III-V族化合物半導體晶圓，其特徵在於，所述III-V族化合物半導體晶圓是磷化銦半導體晶圓。 The III-V compound semiconductor wafer according to claim 16, wherein the III-V compound semiconductor wafer is an indium phosphide semiconductor wafer.