200918461 九、發明說明： 【發明所屬之技術領域】 本發明係關於作爲無機EL元件形成用靶材之硫化鋅成 型體及其製造方法。更詳言之，係關於以硫/鋅之比爲0.9 以上之硫化鋅爲主成分之成型體及其製造方法。 【先前技術】 目前爲止在EL元件之發光層形成，一般係開始使用濺鍍 法或電子束蒸鑛法等的製膜技術。接著在以該等製膜技術 而形成發光層之際，作爲靶材之硫化鋅成型體之製造方法 方面，係將發光性元素混合於硫化鋅粉末之硫化鋅粉末使 用熱壓法進行成型之方法，或使用冷壓法進行成型後，藉 由燒成爐進行燒結之方法等則正在開發中。 但是，硫化鋅粉末結晶性差，要提高成型體之相對密度 (體積密度與理論密度之比）有困難。例如單純以熱壓法成 型之情形，或以冷壓進行預備成型，在單純進行燒結之成 型方法，所得成型體之相對密度只在60〜70%左右。使用 此種相對密度低的成型體以電子束蒸鍍等方法進行製膜之 情形，自硫化鋅成型體釋出氣體，不僅真空度降低，亦有 無法構築發光層等之問題。 因此有提案，將硫化鋅與氧化矽混合，進行熱壓來提高 體積密度之方法（參照專利文獻1)’或有提案使用添加有鋇 成分之硫化鋅粉末藉由冷壓進行成型’在硫化氫氣體中進 行燒成成型之方法（參照專利文獻2)作爲改良之方法。進 200918461 而’將經冷壓之成型體進行熱壓之方法（參照專利文獻3) 爲周知。 【專利文獻1】日本特開平10 — 324968號公報 【專利文獻2】日本特開平2_59463號公報 【專利文獻3】日本特開平5-310467號公報 但是’在專利文獻1記載之方法，因係裝入多量氧化矽 進行成型’雖然相對密度有提高，但矽在製膜時混入。又， 在專利文獻2中，會有鋇混入之問題產生。再者，在專利 文獻2’因在硫化氫中進行燒成成型故會有特殊裝置爲必 要之問題產生。又’在專利文獻3特殊材質之裝置等雖非 必要’但必零使用2種裝置，並無法解決工作時間多且繁 雜之問題。 【發明內容】 發明欲解決之課題 因此，本發明之目的係以工業上有利的方法，提供一種 硫化鋅或含有硫化鋅與銀、銅、錳及稀土元素之至少1種 元素之硫化物之複合硫化物之成型體及其製造方法。 解決課題之手段 本發明人等經戮力硏討，而首先發現藉由複合硫化物之 成型體與其製造方法，該複合硫化物含有，具有接近1之 硫/鋅比的硫化鋅或含有硫化鋅與銀、銅、錳及稀土元素之 至少1種元素之硫化物，而可達成上述目的因而完成本發 明。亦即，本發明係提供以下之物。 200918461 [1 ]—種成型體，其係由複合硫化物所成，該複合硫化 物含有·：硫/鋅之比爲〇. 9以上之硫化辞或含有硫化鋅與銀、 銅I、猛及稀土元素之至少1種元素之硫化物。 [2] 如[丨]記載之成型體，其中該成型體之相對密度爲0.9 以上。 [3] 如IU]或[2]記載之成型體，其中含於該成型體之水分 爲50ppm以下。 [4] 如 Π]〜[3]項中任一項之成型體，其中含於該成型體 之硫酸離子爲500ppm以下。 [5] —種由複合硫化物所成的成型體之製造方法，該複 合硫化物含有：硫化鋅或包含硫化鋅與銀、銅、錳及稀土元 素之至少1種元素之硫化物，其特徵爲將含有粒徑爲1〇〇 // m以下’在比表面積測定中爲〇.2m2/g〜50 m2/g之硫化鋅 或包含硫化鋅與銀、銅、錳及稀土元素之至少1種元素之硫 化物的複合硫化物，在7 00 °C以上1 1 00 °C以下之溫度進行 加壓成型者。 [6] 如[5]記載之成型體之製造方法，其中該含有硫化鋅 或包含硫化鋅與銀、銅、錳及稀土元素之至少1種元素之硫 化物的複合硫化物之X線結晶解析中，2 0 = 3 3 °之繞射峰値 之半高寬爲0.2°〜1.5°。 [7] 如[5]或[6]記載之成型體之製造方法，其中該含有硫 化鋅或包含硫化鋅與銀、銅、錳及稀土元素之至少1種元素 之硫化物之複合硫化物係在水溶液下調製。 200918461 發明效果 本發明之成型體係複合硫化物之成型體，其含有具有@ 於1之硫/鋅比之硫化鋅或含有硫化鋅與銀、_、M s # ± 元素之至少1種元素之硫化物，其可提供一键在卩彡 層之際成爲靶材之具有高成型性之硫化鋅。以T，m _ §3 載更爲簡潔「硫化鋅或含有硫化鋅與銀、銅，_ & g ± % 素之至少1種元素之硫化物之複合硫化物」則單以「複a 硫化物」、「硫化物複合體」等表示。 【實施方式】 實施發明之最佳型態 本發明中，在含有：硫化鋅或含有硫化鋅與銀、銅、鐘 及稀土兀素之至少1種元素之硫化物之複合硫化物方面， 較佳爲可使用含有：可在水溶液下調製之硫化鋅或含有硫 化鋅與銀、銅、鐘及稀土元素之至少1種元素之硫化物的 複合硫化物’或將銀、銅、錳及稀土元素之至少1種元素之 硫化物混合於在水溶液下所調製之硫化鋅所得之複合硫化 物。 在水溶液下之調製方法方面，並無特別限制，若爲使含 有鋅之鹽與硫化劑反應之方法，則以鹼性、酸性之任一條 件製作之物亦無妨。例如，藉由將硝酸鋅之水溶液與硫化 鈉水溶液在室溫下混合亦可進行調製，在硝酸鋅之水溶液 添加硫代乙醯胺，於1 〇〇 t左右之溫度下使之反應而調製亦 200918461 在含有於液相下調製使用之鋅的鹽方面，可使用氯化鋅、 溴化鋅等鹵化物、硫酸鋅、亞硫酸鋅磷酸鋅、硝酸鋅、 碳酸鋅等礦酸鹽、或甲酸鋅、乙酸鋅、草酸鋅等有機酸鹽。 該等，可爲無水鹽而爲含水鹽亦無妨。該等可作單一使用 而混合使用亦無妨。在使用之鹽純度方面，並無特別限制 以越高越好’特別是可使用不含鐵、鎳、鈷、鉻、鎢等金 屬不純物之物，在將所得成型體使用於螢光體之製造之情 形爲佳。 在液相下調製複合硫化物之情形，將至少1種銀、銅、 錳及稀土元素之鹽，添加於含有鋅之鹽來調製複合硫化 物。可因應需要，相對於作爲受體（acceptor)之銀、銅、錳 及稀土元素元素，可作爲予體作用，使鋁、鎵、銦、氯、 溴等元素存在於液相中，此種予體元素則需於複合硫化物 中擷取。 銀、銅、錳及稀土元素之鹽以及供體元素之鹽方面，可 使用上述鹵素鹽、礦酸鹽、有機酸鹽，該等可爲無水鹽而 爲含水鹽亦無妨。該等可單一使用而混合使用亦無妨。使 用之鹽之純度方面’並無特別限制之物，但以越高者越佳， 尤其是使用不含鐵、鎳、鈷、鉻、鎢等之金屬不純物者， 就將所得成型體使用於螢光體之製造之情形爲佳。 相對於含於複合硫化物中之銀、銅、錳及稀土元素元素 以及作爲受體之銀、銅、鑑及稀土元素元素，作爲供體而 作用之元素之量方面’並無特別限制，但過多的量，因激發 200918461 子彼此間之相互作用會使螢光收率降低故不佳，過少的 量’因取出之螢光量降低故不佳。因此，以含有50〜 50,000ppm’ 較佳爲 100 〜40,000ppm，更佳爲 300 〜30,000ppm 之範圍爲恰當。 本發明中所使用之硫化劑方面，可使用硫化氫、硫化鋰、 硫化鈉、硫化鉀等鹼金屬硫化物，硫代甲醯胺、硫代乙醯 胺等之硫代醯胺類’硫脲等。該等硫化劑之使用量方面， 不用說因其適用方法而異，通常相對於使用之鋅鹽，爲〇.1 〜5當量之範圍’考慮到硫化物之生成效率、經濟性，以 使用0.5〜3當量爲佳，更佳爲0.8〜2當量。 本發明中，液相調製以在水中實施爲佳。爲了將所得硫 化物作爲螢光體使用，以不含爲必要之金屬以外者爲佳。 因此，使用之水以使用離子交換水爲佳，鐵、鎳、鈷等重 金屬各自爲50ppm以下，較佳爲l〇ppm以下，鈉、鉀、鈣、 鎂等典型金屬各自爲500ppm以下，較佳爲l〇〇ppm以下之 物。 在液相調製之際，可存在於液相中作爲硫酸鎂等粒徑調 整劑（利用電解質所致凝集效果）使用之金屬鹽。此種金屬 因洗淨等最終而言，還是不能在硫化物中擷取。 液相調製中反應溫度因使用之硫化劑而異，而在過低之 溫度，因反應之進行顯著緩慢故不佳，在過高之溫度，在 發生之硫化氫之液中濃度降低，因硫化劑效率降低故不 佳。通常可在5°C〜120°C，更佳爲10°C〜100°C之範圍實 -10- 200918461 施。反應之方式亦無特別限定，可採用批次式、連續式之 任一種方法均無妨。 液相調製中所得之硫化物，可以傾析或離心分離等方法 與水分離，同時重覆離子交換水之洗淨，進行洗淨使水洗 層之pH成爲6〜8。 所洗淨之硫化物，可以真空乾燥或1 5 0°C以下之熱風乾燥 等之方法將水除去，並乾燥之。乾燥時間方面，不用說係 取決於所含水之量，而通常爲1小時〜50小時，考慮到乾 燥之效率，可在1.5小時〜20小時之範圍實施。 在本發明含於所得成型體之水分量以50ppm以下爲佳。 水分量多時，在用於濺鍍法等情形，因金屬硫化物被氧 化故不佳。因此較佳爲1〜30ppm，更佳爲1〜20ppm。因此， 在乾燥完成時（加壓成型前）之硫化物複合體中水分在lppm 〜2000ppm之範圍，更佳爲10〜lOOOppm。 在含於本發明所得成型體之硫酸離子濃度方面，以 5 OOppm以下爲佳。硫酸離子多時，在用於濺鍍法等之情形， 金屬硫化物被氧化，或混入於薄膜中，因成爲腐蝕或分解 之原因故不佳。因此，在成型體中硫酸離子濃度方面爲1 〜200ppm之範圍，更佳爲1〜lOOpprn之範圍。因此在洗淨’ 乾燥完成時（加壓成型前）之硫化物複合物中硫酸離子濃度 方面，以lppm〜2000ppm範圍爲佳，爲了穩定而使硫酸離 子濃度在目的之範圍，則以1〜600ppm之範圍更佳。 200918461 在硫化鋅中添加至少一種銀、銅、錳及稀土元素鹽之金 屬，來調製混合硫化物之情形，可使用各種金屬硫化物。 該等可單一使用亦可混合使用均無妨。使用之硫化物之純 度方面，並無特別限制之物，但以越高者越佳’尤其是使 用不含鐵、鎳、鈷、鉻、鎢等金屬不純物者，將所得成型 體使用於螢光體之製造之情形爲佳。 所得硫化物之比表面積以0.2 m2/g〜50 m2/g爲佳。比表 面積過小時，在成型時想要熔合（fusing)也無法發生充分的 硫蒸氣壓，因無法黏合故高的溫度或長時間之成形爲必 要，結果或發生硫成分之脫落，或造成缺損故不佳。又’ 具有過寬的比表面積時，與成型時之溫度上昇同時，一邊 有顯著的硫蒸氣壓上升，一邊並無法達到可黏合之溫度， 故在達到設定之溫度以前，發生硫之欠缺，結果引起硫缺 乏故不佳。 又，所得硫化物，以X線結晶解析進行分析，在使用2 0 =3 3°所觀測之信號値之一半高寬爲0.2°〜1.5°之範圍內之 物進而爲佳。在0.2°以下，結晶性過高，因在加熱/加壓成 型之成形性會惡化故不佳。又，超過1 . 5 °時，結晶性過低’ 在燒結時會倂發分解等，而使結晶性提高之處理會成爲必 要。 本發明中，所得之硫化物，可因應需要，進行加熱燒成。 藉由此燒成，可將含於複合硫化物中之水分除去，或促進 硫酸離子之分解。 -12- 200918461 一方面’可提局硫化物結晶化度’而提 比表面積會顯著降低，因會促成結晶化 故有留意之必要。又，過於低時，無法 就只有步驟之複雜化。加熱之溫度，因 法而定當然不用特定，而通常在20CTC， 佳爲300°C〜600°C之範圍實施。 燒成之時間並無特別限定，可因應目 在0.5〜10小時之範圍，在考慮裝置之 可在1〜8小時之範圍實施。通常，燒成 還原氛圍下實施者爲當然。方法方面， 續式之任一種方法均無妨。 在本發明’燒成之氛圍方面，並無特 在因會引起複合硫化物表面氧化故不佳 圍下，或還原氛圍下實施。在還原氛圍 在下’可在複合硫化物中添加硫進行燒 構造而定’但考慮安全性，以在複合硫 燒成爲佳。藉此，可進而提高含於複合 硫酸離子之除去效率。 燒成時硫添加量方面並無特別限定， 硫化物100重量份，可添加0.1〜20重量 機器穩定性，爲0 · 2〜1 5重量份，更佳ί 添加之方法方面，將固體彼此之間混合 於二硫化碳等溶劑，與複合硫化物混合 高至必要以上時， 且因無法加壓成形 獲得加熱之效果， 依液相調製時之方 - 800 °C之範圍，較 的而變化，但通常 加熱、冷卻能力， 係在惰性氛圍下或 可採用批次式或連 別限定，但氧之存 ，而在惰性氣體氛 方面，於硫化氫存 成。可因燒成爐之 化物中添加硫進行 硫化物中之水分或 通常，相對於複合 份，在考慮操作性、 i 〇. 3〜1 〇重量份。 亦無妨，將硫溶解 ，予以乾燥亦無妨。 -13- 200918461 再者，在本發明，使燒成在真空下實施亦無妨。在於真 空下處理之溫度方面，並無特別限定，在過高之溫度，因 會助長所添加硫之蒸散（evaporating)，或複合硫化物表面硫 之欠缺並不佳，通常可在100〜400°C之範圍，更佳爲100 °C〜3 00°C之範圍實施。藉此可將附著於複合硫化物之氧， 水分有效的除去，而可抑制燒成中氧化所致硫酸離子增 加。在減壓度方面，並無特別限定，通常，可在1〜6QKPa 之範圍實施。 所得之燒成物，可因應需要，進行粉碎分級，使用於成 型，可因應需要，以酸、離子交換水等洗淨，可將生成於 表面之氧化物除去。在進行此種洗淨之情形，可重新以真 空，熱風等方法進行乾燥。 本發明中，在成型之前，爲了提高硫化物預先成型時之 流動性、壓縮性則成爲粉體。粉體之粒度方面，以可維持 成型時之流動性之範圍爲佳，通常爲1 00 // m以下，更佳爲 70 // m以下，在考慮到對成型機之負荷時以50 // m以下， 尤以40 # m以下爲佳。粉碎之方法方面並無特別限定，亦 可使用硏缽所致粉碎，球磨機、渦輪式硏磨機、旋風硏磨 機等之方法。 本發明中，所得之硫化物係裝入熱壓成形型（模具），經 壓力與溫度之處理而成型。本發明中，加熱、加壓成型之 方法方面，可使用熱壓法、放電燒結法等任一種方法均無 妨。熱壓之成形型之材質方面，可使用碳、氧化鋁、賽龍 -14- 200918461 (sialon)等。尤其是在與硫化物之反應爲顯著的情形，將賽 龍、碳等表面使用玻璃等非反應物經塗膜之物亦無妨。 本發明中，在熱壓成型之際進行加壓之壓力方面，並無 特別限定，爲了提高相對密度以100Kg/cm2〜500Kg/cm2加 壓而構築成型體。 過低之壓力，因無法提高相對密度，並不佳，過高之壓 力因會損及粒子強度故不佳。 本發明中，在熱壓成型之際加熱之溫度方面，可在600 °C〜1 1 00 °C之範圍實施。在過低之溫度，因無法產生粒子 之黏合故不佳，在過筒之溫度，粒子之結晶化爲大，因成 形體內空隙（void)之發生變多故不佳。因此，在700°C〜1050 °C之範圍，更佳爲在800°C〜1000°C之範圍實施。 本發明中，成形之順序方面，並無特別限制。例如添加 硫化物於模具，可因應需要添加硫並裝入，安裝成形夾具， 一次減壓至140Pa左右。減壓係以氬開放，重覆此操作， 將含於硫化物複合體內之氧，及附著於硫化物複合體表面 之水分除去。 接著，將硫化物放置於減壓中之狀態開始機械式加壓， 設定之機械壓力（壓機壓力）在施加於硫化物，則保持1分 〜1小時左右。因此，相對於硫化物之減壓係以氬開放， 在壓機壓力施加於硫化物之狀態下開始升溫。 在設定之溫度，保持1分〜1小時後，開始降溫，於回 復至室溫之階段，解除壓機壓力，亦可獲得目的之成型體， -15- 200918461 在升溫後開放減壓之方法，可採用在降溫時解除壓機壓力 而冷卻之方法亦無妨。所得之成型體自模具卸下後，可因 應需要實施硏磨等處置，可容易地作爲濺鍍用靶使用。以 下’試例舉實施例詳細說明本發明，但本發明並非限定於 以下之實施例。 實施例1 取硝酸鋅六水合物232.2g、硫酸鎂4.5g、硝酸銅三水合 物1.39g、硝酸鎵八水合物3.35g於2L可分離燒瓶，添加 離子交換水750g並溶解之。對此添加硝酸l_5g，將系統中 pH調整至2左右，在此燒瓶安裝攪拌器、溫度計、回流管， 一邊攪拌已調整pH之液，一邊升溫至90 °C爲止。在達到 設定溫度時，添加固體之硫脲8 4.5 g。添加完成後，經2小 時攪拌後，爲使反應停止，將系統內冷卻至30 °C。在冷卻 中，通入氮氣流，使系統內之硫化氫排氣。 自所得之反應液以傾析將反應液除去，進而用離子交換 水進行殘留固體之洗淨，進行洗淨使洗液之p Η爲6左右。 將洗淨完成之固體，在1 5 (TC進行1 2小時熱風乾燥，再者， 在120 °C進行真空乾燥，獲得摻雜有銅的硫化鋅複合體 58.5g 。 所得之硫化鋅複合體係粒徑D 5 0 (中心粒徑）爲1 2 // m之 粉末。在此粒度分布係使用堀場製作所製LA-95 0，使分营女 於水溶劑並測定之。將所得粉末，使用日本 B e 11公司g BELSORP18，藉由氮吸附測定比表面積測定，則爲 4〇/ -16 - 200918461 m2/g。又將所得粉末以XRD測定，貝[]2 0 =33°之半高寬爲 1.273。。 水分量係使用電量滴定法卡氏（Karl Fischer)水分計（三菱 化成公司製：型式 VA-06)測定，結果所得之水分量爲 892ppm ° 硫酸離子分析係以離子色譜法（ion chromatogramphy)法 (島津製作所製：型式HIC-SP)來實施。 將20mg樣本溶解於5.0g鹽酸，予以完全溶解後，通過 氮氣體，使鹽酸揮發，添加離子交換水，成爲10.0g。所檢 測之硫酸離子量爲5 62ppm。 裝入所得硫化鋅複合體12g於30mm〇)模具，塡充於熱壓 機。將模具內減壓至1 3 0 P a ’保持1 〇分鐘，減壓係用氬於 常壓開放。此操作實施3次，將模具內之減壓以氬氣體在 常壓開放，使壓機壓力（200Kg/c m2)施加於硫化鋅複合體， 同時經1小時升溫至9 0 0 °C。升溫後解除壓機壓力，以2 小時冷卻至室溫。自模具使成型體脫開，獲得3 0 m m Φ、厚 度5.49mm之圓筒形靶材。 收集所得靶材之一部份，以1 N鹽酸溶解，以乙二胺四乙 酸（EDTA)溶液滴定’來定量金屬含量。定量結果爲硫/鋅 =〇 · 9 7。所得靶之體積密度爲3 · 8 8 g / c m3，相對密度（體積密 度與理論密度之比。理論密度係使用硫化鋅原來之密度 4.0g/cm3)爲0.97。水分量爲41ppm、硫酸離子量爲22ppm。 實施例2 -17- 200918461 在實施例1所得經液相調製之摻雜有銅的硫化鋅30g添 加硫6g，於氮下，在50(TC經3小時加熱燒成，冷卻至室 溫。所得之硫化鋅複合體係粒徑D 5 0爲1 8 v m之粉未。所 得之粉末進行比表面積測定，則爲0 · 6 5 m2 / g。所得之粉末 以XRD測定，則20 =33。之半高寬爲0.415。。又，水分量爲 128ppm、硫酸離子量爲255ppm。 將所得硫化鋅複合體12g裝入30ιηιηΦ之模具，充;塡於熱 壓機。在模具內減壓至130Pa，保持10分鐘，使用開放 至常壓。此等操作實施3次，將模具內之減壓以氬氣體開 放至常壓，將壓機壓力（2 00Kg/c m2)施加於硫化鋅複合體以 1小時升溫至900°C。升溫後解除壓機壓力，以2小時冷卻 至室溫。 自模具解開成型體，獲得30ιηιηΦ、厚度5.37mm之圓筒 形靶材。採用所得靶材之一部份，以1 N鹽酸溶解，以EDTA 溶液滴定，在定量金屬含量之結果爲硫/鋅=〇 . 9 5。所得¥巴之 體積密度爲3.75g/cm3、相對密度（體積密度與理論密度之比） 爲0.95。又，水分量爲49ppm、硫酸離子量爲41ppm。 實施例3 在實施例2中’除了以8 00 °C燒成以外，其他與實施例2 同。所得硫化辞複合體fii徑D50爲28/zm之粉末。所得粉 末進行比表面積測定則爲〇 . 2 2 m2 / g。將所得之粉末進行 XRD測定則2 0 =33°之半高寬爲0.3 7 5°。又，水分量爲 118ppm、硫酸離子量爲221ppm。 -18- 200918461 將所得硫化鋅複合體12g裝入30ιηιηΦ之模具，充塡於熱 壓機。使模具內減壓至13 OPa，保持10分鐘，使用氬開放 至常壓。此操作實施3次，模具內之減壓以氬氣體開放， 將壓機壓力（200Kg/c m2)施加於硫化鋅複合體同時升溫1小 時至900°C爲止。升溫後解除壓機壓力，以2小時冷卻至室 溫。 使成型體自模具脫離，獲得30mm0>、厚度5.20 mm之圓 筒形靶材。 採用所得之靶材之一部份，以1 N鹽酸溶解，以EDTA溶 液滴定，定量金屬含量，結果爲硫/鋅=0.92。所得靶之體積 密度爲3.73g/cm3、相對密度（體積密度與理論密度之比）爲 0.94。又，水分量爲33ppm、硫酸離子量爲51ppm。 實施例4 除了在實施例1中，金屬鹽係僅使用硝酸鋅六水合物 2 3 2.2g以外，其他之實施則與實施例1同，獲得硫化鋅 57.1g。所得硫化鋅係粒徑D50爲16 // m之粉末。所得之粉 末進行比表面積測定則爲4 0.3 m2 / g。 將所得之粉末進行X RD測定則2 0 = 3 3 °之半高寬爲1 . 3 7 1 °。又，水分量爲994ppm、硫酸離子爲557ppm。 將硫化錳0.05g混合於上述所得之硫化鋅粉末20g，使用 Thinky公司製混合機ARE-250，進行2000次旋轉，30秒混 合。將所得之硫化鋅混合物12g裝入30mm Φ之模具，充塡 於熱壓機。使模具內減壓至130Pa，保持1〇分鐘，以氬解 -19- 200918461 放至常壓。此操作實施3次，使模具內之減壓以氬氣體開 放至常壓，將壓機壓力（200Kg/c m2)施加於硫化鋅複合體同 時經1小時升溫至900°C。升溫後解除壓機壓力，以2小時 冷卻至室溫。 使成型體自模具脫離，獲得30mm Φ、厚度5.26mm之圓 筒形靶材。採用所得靶材之一部份，以1N鹽酸溶解，以 EDTA溶液滴定，定量金屬含量，結果爲硫/鋅=0.94。所得 之靶之體積密度爲3.72 g/cm3、相對密度（體積密度與理論密 度之比）爲0.93。又，水分量爲27ppm、硫酸離子量爲32ppm。 實施例5 將硫6 g添加於實施例4所得硫化鋅混合物3 0 g，在氮下， 以600 °C經3小時加熱燒成，冷卻至室溫。所得之硫化鋅係 粒徑D50爲32 // m之粉末。所得之粉末進行比表面積測定 則爲〇.221112/2。將所得之粉末進行乂1^測定則20=33°之 半高寬爲 0.265 ° 。又水分量爲 1 13ppm、硫酸離子量爲 245ppm ° 將所得硫化鋅12g裝入之模具充塡於熱壓機。使 模具內減壓至130Pa，保持10分鐘，以氬解放至常壓。此 操作實施3次，將模具內之減壓以氬氣體開放至常壓，將 壓機壓力（200 Kg/cm 2)施加於硫化鋅複合體，同時以1小時 升溫至900 °C。升溫後解除壓機壓力’以2小時冷卻至室溫。 使成型體自模具脫離’獲得30ηιιηΦ、厚度5.15mm之圓 筒形靶材。 -20- 200918461 採用所得之靶材之一部份，以IN鹽酸溶解，以EDTA溶 液滴定，定量金屬含量，結果爲硫/鋅=0.93。所得靶之體積 密度爲3.66g/cm3、相對密度（體積密度與理論密度之比）爲 0.91。又，水分量爲44ppm、硫酸離子量爲57ppm。 實施例6 在實施例2中，除了使硫化鋅複合體在40CTC燒成，加熱 成型在8 5 0 °C實施以外，其他之進行則同於實施例2。所得 之硫化鋅複合體粉末進行比表面積測定則爲0.89 m2/g。所 得之硫化鋅複合體係粒徑D 5 0爲1 6 // m之粉末。所得之粉 末進行XRD測定則2 0 =3 3°之半高寬爲0.665°。 又，水分量爲128ppm、硫酸離子量爲255ppm。 採用所得之圓筒形IE材之一部份，以1N鹽酸溶解，以 EDTA溶液滴定，定量金屬含量，結果爲硫/鋅二1.〇5。所得 靶之體積密度爲3.87g/cm3、相對密度（體積密度與理論密度 之比）爲0.96。又’水分量爲35ppm、硫酸離子量爲55ppm。 實施例7 在實施例2中，除了使硫化鋅複合體在70(rc燒成，使加 熱成型在7 5 0 °C實施以外，其他之進行則同於實施例2。所 得之硫化鋅複合體粉末進行比表面積測定則爲〇.丨8 m2/g。 所得之硫化辞複合體係粒徑D 5 0爲1 9 /z m之粉末。所得之 粉末進行XRD測定則20 =33。之半高寬爲〇.224。。又，水分 量爲96ppm、硫酸離子量爲I38ppm。 -21 - 200918461 採用所得之圓筒形靶材之一部份，以1N鹽酸溶解，以 EDTA溶液滴定，定量金屬含量，結果爲硫/鋅=0.91。所得 靶之體積密度爲3.56g/cm3、相對密度（體積密度與理論密度 之比）爲0.89。又，水分量爲21ppm、硫酸離子量爲44ppm。 比較例1 實施例3中，除了添加硫6 g及氯化鈉1.5 g於實施例1 所得經液相調製之摻雜銅的硫化鋅複合體30g以外，其他 之進行則同於實施例3。所得之硫化鋅複合體係粒徑D50 爲28# m之粉末。所得之粉末進行比表面積測定則爲0.12 m2/g。所得之粉末進行XRD測定則2 0 =33°之半高寬爲〇. 183 °。又，水分量爲88ppm、硫酸離子量爲89ppm。 將所得之硫化鋅複合體12g裝入30ιηιηΦ之模具，充塡於 熱壓機。使模具內減壓至130Pa，保持10分鐘，以氬解放 至常壓。此操作實施3次，模具內之減壓係以氬氣體開放 至常壓，將壓機壓力（200Kg/cm2)施加於硫化鋅複合體，同 時以1小時升溫至900t。升溫後解除壓機壓力，以2小時 冷卻至室溫。 使成型體自模具脫離，獲得30mmCP、厚度4.92mm之圓 筒形靶材。採用所得之靶材之一部份，以1 N鹽酸溶解，以 EDTA溶液滴定，定量金屬含量，結果爲硫/鋅=〇.87。所得 靶材之體積密度爲3.41 g/cm3、相對密度（體積密度與理論密 度之比）爲0.85。又，水分量爲22ppm、硫酸離子量爲41ppm。 比較例2 -22- 200918461 將攪拌器、回流管、溫度計安裝於5升三口燒瓶，取硝 酸鋅六水合物149.1g、硝酸銅三水合物〇.〇926g、硝酸鎵五 水合物〇.1246g，添加1升離子交換水並溶解之，成爲在氮 氣流下。對此經20分鐘添加使硫化鈉九水合物145.5g溶解 於離子交換水1升之水溶液。反應溫度爲27 °C，進而攪拌 2小時。 自所得之反應液以傾析除去反應液，再使用離子交換水 進行洗淨，進行洗淨使洗液之pH成爲6左右。將完成洗淨 之固體於1 50°C進行1 2小時熱風乾燥，獲得摻雜有銅的硫 化鋅41 . lg。所得之硫化鋅複合體係粒徑D50爲30 // m之粉 末。將所得之粉末進行比表面積測定則爲1 05.2 m2/g。將所 得之粉末進行XRD測定則2Θ =33°之半高寬爲2.22°。又， 水分量爲2450ppm、硫酸離子爲1266ppm。 將所得之硫化鋅複合體12g裝入 30ιηιηΦ之模具，充塡 於熱壓機。使模具內減壓至130Pa，保持10分鐘，以氬解 放至常壓。此操作實施3次，模具內之減壓係以氬氣體開 放至常壓，將壓機壓力（200 Kg/c m2)施加於硫化鋅複合體， 同時以1小時升溫至900°C。升溫後解除壓機壓力，以2 小時冷卻至室溫。使成型體自模具脫離，卻固著於模具， 而無法獲得目的物。水分量爲 899ppm、硫酸離子量爲 4 4 7 p p m ° 比較例3 將硫6 g添加於實施例1所得經液相調製之摻雜有銅之硫 -23- 200918461 化鋅複合體3 0 g，在氮下，以2 5 0 °C進行3小時加熱燒成， 冷卻至室溫。所得硫化鋅複合體係粒徑D 5 0爲6 2 // m之粉 末。所得之粉末進行比表面積測定則爲5 0.3 3 m2 / g。所得之 粉末進行X R D測定則2 0 = 3 3 °之半高寬爲1. 8 1 °。又，水分 重爲1227ppm、硫酸離子量爲723ppm。 將所得之硫化鋅複合體12g裝入30mm〇>之模具，充塡於 熱壓機。使模具內減壓至130Pa，保持10分鐘，以氬解放 至常壓。此操作實施3次，模具內之減壓係以氬氣體開放 至常壓’壓機壓力（200Kg/c m2)施加於硫化鋅複合體，同時 以1小時升溫至900°C。升溫後解除壓機壓力，以2小時冷 卻至室溫。使成型體自模具脫離，但是成型體之一部份固 著於模具壁面，在取出靶之際，自固著部分產生剝離，而 無法維持目的之靶形狀。水分量爲1 0 1 1 p p m、硫酸離子量 爲 5 1 2 p p m ° 比較例4 將硫6 g、氯化鈉1 · 5 g添加於實施例4所得硫化鋅混合物 3 Og並混合，在氮下，以1 000 °C進行3小時加熱燒成，冷 卻至室溫。所得之硫化鋅複合體係粒徑D 5 0爲3 5 // m之粉 末。將所得之粉末進行比表面積測定則爲0.09 m2/g。所得 之粉末進行X R D測定則2 β = 3 3 °之半高寬爲〇 . 1 8 3 °。又，水 分量爲64ppm、硫酸離子量爲66ppm。 將所得之硫化鋅複合體12g裝入30ιηιηΦ之模具，充塡於 熱壓機。使模具內減壓至130Pa，保持10分鐘，以氬解放 -24- 200918461 至常壓。此操作實施3次，模具內之減壓係以氬氣體開放 至常壓，壓機壓力（200Kg/c m2)施加於硫化鋅複合體，同時 以1小時升溫至900 °C爲止。升溫後解除壓機壓力，以2 小時冷卻至室溫。 使成型體自模具脫離，獲得30ιηιηΦ、厚度3mm之圓筒形 靶材。採用所得之靶材之一部份，以1 N鹽酸溶解，以E D T A 溶液滴定，定量金屬含量，結果爲硫/鋅=0.86。所得之靶材 之體積密度爲3.41g/cm3、相對密度（體積密度與理論密度之 比）爲0.85。又，水分量爲35ppm、硫酸離子量爲31ppm。 比較例5 實施例2中，除了使複合硫化物以7 0 0 °C燒成，加熱成型 以1 0 0 0 °C實施以外，其他之進行則同於實施例2。所得硫 化辞複合體係粒徑D50爲22// m之粉末。所得之粉末進行 比表面積測定則爲0· 1 8 m2/g。所得之粉末進行XRD測定則 20 =33°之半高寬爲0.223°。又，水分爲96ppm、硫酸離子 爲 1 3 8 p p m ° 在成型後，取圓筒形靶材之一部份，以1 N鹽酸溶解，以 EDTA溶液滴定，定量金屬含量，結果爲硫/鋅=0.88。所得 靶之體積密度爲3.76g/cm3、相對密度（實測密度與理論密度 之比）爲0.94。又’所得成型體之水分量爲I9ppm、硫酸離 子量爲37ppm。 比較例6 -25- 200918461 在比較例4中，除了將硫化鋅複合體在1 l〇〇°C經加熱燒 成以外，其他之實施則同於比較例4。所得之硫化鋅複合體 係粒徑D50爲38 // m之粉末。所得之硫化鋅複合體粉末進 行比表面積測定則爲0.08 m2/g。2 0 =3 3°之半高寬爲0.144°。 又，水分量爲12ppm、硫酸離子量爲38ppm。 將所得之硫化鋅複合體12g裝入30ιηιηΦ之模具，充塡於 熱壓機。使模具內減壓至130Pa，保持10分鐘，以氬解放 至常壓。此操作實施3次，模具內之減壓係以氬氣體開放 至常壓，壓機壓力（200Kg/c m2)施加於硫化鋅複合體，同時 以1小時升溫至900°C。升溫後解除壓機壓力，以2小時冷 卻至室溫。 使成型體自模具脫離，獲得3〇ΓηιηΦ、厚度4.35mm之圓 筒形靶材。 採用所得之靶材之一部份，以1 N鹽酸溶解，以EDTA溶 液滴定’定量金屬含量，結果爲硫/鋅=0.82。所得靶材之體 積密度爲3.07g/cm3、相對密度（體積密度與理論密度之比） 爲0.77。又’水分量爲I5ppm、硫酸離子量爲33ppm。 實施例8 取硝酸鋅六水合物3 6 0.0 g、硫酸鎂7.2 g、0.1 Μ硝酸銀水 溶液57. OmL、硝酸鎵八水合物3.66g於2升可分離燒瓶， 添加離子交換水丨2 〇 0 g予以溶解。對此添加硝酸1 . 5 g，使 系中pH調整於2左右。在此燒瓶，安裝攪拌器、溫度計、 回流管’一邊攪拌已調整pH之液，一邊升溫至9(TC。達 -26- 200918461 到設定之溫度則添加硫代乙醯胺133.6g之固體。添加完成 後’經2小時攪拌後，爲使反應停止，將系統內冷卻至3 0 °C。冷卻中，通入氮氣流，將系內之硫化氫排出。自所得 之反應液以傾析將反應液除去，進而以離子交換水進行殘 留固體之洗淨，進行洗淨使洗液之pH成爲5以上。將經洗 淨完成之固體’以1 5 0 °C經1 2小時熱風乾燥，獲得摻雜銀 的硫化鋅複合體93.5g。所得硫化鋅複合體係粒徑D50爲 I 6 μ m之粉末。所得之粉末進行X線繞射（XRD)測定則2 Θ = 33°繞射峰値之半高寬爲1.363°。又，水分爲612ppm、硫 酸離子爲447ppm 。 將上述所得之硫化鋅複合體粉末12g裝入30ιηιηΦ之模 具，充塡於熱壓機。使模具內減壓至130Pa，保持10分鐘， 減壓係以氬開放至常壓。此操作實施3次，模具內之減壓 係以氬氣體開放至常壓，使壓機壓力（200Kg/c m2)施加於硫 化鋅複合體，同時以1小時升溫至9 0 0 °C。 升溫後解除壓機壓力，以2小時冷卻至室溫。使成型體 自模具脫離，獲得30mm Φ，厚度5.49mm之圓筒形靶材。 所得靶材之體積密度爲3.89g/cm3，相對密度爲0.97。取所 得圓筒形靶材之一部份，以1N鹽酸溶解，以EDTA溶液滴 定，定量金屬含量，結果爲硫/鋅=0.92。又，水分量爲 24ppm、硫酸離子量爲46ppm。 實施例9 實施例8中，除了硫酸鎂之使用量爲2.5g，硝酸之使用量 -27- 200918461 爲0.5g，使洗淨完成之固體之乾燥溫度爲200°C以外，其{也 之實施則同於實施例8，獲得摻雜銀之硫化鋅複合體9 k 5 g。 所得硫化鋅複合體係粒徑D 5 0爲6 7 // m之粉末。其硫化鲜複 合體粉末之2Θ =33°之繞射峰値之半高寬爲1.333。。又，水 分爲506ppm、硫酸離子量爲417ppm。將此粉末與實施例8 同樣地壓製獲得30ιηιηΦ、厚度5.09mm之圓筒形祀材。所得: 靶材之體積密度爲3.6 lg/cm3、相對密度爲0.90。採用所得圓 筒形靶材之一部份，以1 N鹽酸溶解，以EDTA溶液滴定， 定量金屬含量，結果硫/鋅=0.93。又，水分量爲26ppm、硫 酸離子量爲48ppm。 比較例7 在實施例2中，除了添加氯化鈉1 .5 g及氯化鎂3 g於硫 化鋅複合體粉末12g，以1100 °C加熱燒成以外，其他之實 施同於實施例2，獲得燒成後之硫化鋅複合體。所得硫化 鋅複合體係粒徑D50爲104# m之粉末。其硫化鋅複合體粉 末之20 =33°之繞射峰値之半高寬爲0.198°，水分爲 7 7ppm，硫酸離子量爲67 ppm。將此粉末與實施例2同樣地 壓製獲得30mm Φ、厚度4.52mm之圓筒形靶材。所得靶材 之體積密度爲3.2Og/cm3、相對密度爲0.80。採用所得圓筒 形靶材之一部份，以1 N鹽酸溶解，以EDTA溶液滴定，定 量金屬含量，結果爲硫/鋅=0.88。又，水分量爲21ppm、硫 酸離子量爲33ppm。 -28- 200918461 【表1】 表1:乾燥完成時硫化鋅或複合硫化物之實驗數據 D50 (/zm) 比表面積 (m2/g) 2 0=33° 半高寬(° ) 水份 (ppm) 硫酸離子 (ppm) 實施例1 12 40.2 1.273 892 562 實施例2 18 0.65 0.415 128 255 實施例3 28 0.22 0.375 118 221 實施例4 16 40.3 1.371 994 557 實施例5 32 0.22 0.265 113 245 實施例6 16 0.89 0.665 128 255 實施例7 19 0.18 0.224 96 138 實施例8 16 1.363 612 447 實施例9 67 1.333 506 417 比較例1 28 0.12 0.183 88 89 比較例2 30 105.2 2.22 2450 1266 比較例3 62 50.33 1.81 1227 723 比較例4 35 0.09 0.18 64 66 比較例5 22 0.18 0.223 96 138 比較例6 38 0.08 0.144 12 38 比較例7 104 0.198 77 67 -29- 200918461 【表2】 表2:成型體之實驗數據 硫/鋅 相對密度 水份 (ppm) 硫酸離子 (ppm) 實施例1 0.97 0.97 41 22 實施例2 0.95 0.95 49 41 實施例3 0.92 0.94 33 51 實施例4 0.94 0.93 27 32 實施例5 0.93 0.91 44 57 實施例6 1.05 0.96 35 55 實施例7 0.91 0.89 21 44 實施例8 0.92 0.97 24 46 實施例9 0.93 0.90 26 48 比較例1 0.87 0.8 1 22 41 比較例2 無法取得 899 447 比較例3 無法取得 1011 512 比較例4 0.86 0.85 35 31 比較例5 0.88 0.94 19 37 比較例6 0.82 0.77 15 33 比較例7 0.88 0.80 21 33 [產業上之利用可能性] 根據本發明係提供一種含有，具有近於I之硫/鋅比的硫 化鋅或含有硫化鋅與銀、銅、錳及稀土元素之至少1種元 素之硫化物的，具有高成型性的複合硫化物之成型體。此 種成型體在形成發光層之際’作爲靶材爲有用。又，根據 -30- 200918461 本發明之成型體之製造方法，可使此種成型體以高生產性 進行生產，產業上爲有用。 【圖式簡單說明】 Μ 。 j \ \\ 【主要元件符號說明】 Μ 。[Technical Field] The present invention relates to a zinc sulfide molded body as a target for forming an inorganic EL element and a method for producing the same. More specifically, the ratio of sulfur to zinc is 0. A molded body of 9 or more zinc sulfide as a main component and a method for producing the same. [Prior Art] Conventionally, a light-emitting layer of an EL element has been formed, and generally, a film forming technique such as a sputtering method or an electron beam evaporation method has been used. Next, in the method of producing a zinc sulfide molded body as a target, a method of producing a zinc sulfide molded body as a target by mixing the zinc sulfide powder of the zinc sulfide powder by a hot press method in the method of producing the light-emitting layer by the film forming technique After the molding by cold pressing, a method of sintering by a firing furnace is being developed. However, zinc sulfide powder has poor crystallinity, and it is difficult to increase the relative density (ratio of bulk density to theoretical density) of the molded body. For example, in the case of molding by hot pressing alone or by preliminary molding by cold pressing, the relative density of the obtained molded body is only about 60 to 70% in the molding method in which sintering is simply performed. When such a film having a relatively low density is formed by a method such as electron beam evaporation, the gas is released from the zinc sulfide molded article, and the degree of vacuum is lowered, and the problem of the formation of the light-emitting layer or the like is not caused. Therefore, there is a proposal to mix zinc sulfide with cerium oxide and perform hot pressing to increase the bulk density (see Patent Document 1) 'or it is proposed to use cold-pressed zinc sulfide powder added with a cerium component to form hydrogen sulfide. A method of performing firing molding in a gas (see Patent Document 2) is an improved method. The method of hot pressing a cold-pressed molded body (see Patent Document 3) is known. [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. A large amount of cerium oxide is formed for molding. Although the relative density is improved, yttrium is mixed during film formation. Further, in Patent Document 2, there is a problem that entanglement occurs. Further, in Patent Document 2', a special device is required to be formed by firing in hydrogen sulfide. Further, in the case of a device of a special material of Patent Document 3, it is not necessary to use two types of devices, and it is not possible to solve the problem of a large number of complicated working hours. SUMMARY OF THE INVENTION PROBLEMS TO BE SOLVED BY THE INVENTION Accordingly, it is an object of the present invention to provide a composite of zinc sulfide or a sulfide containing zinc sulfide and at least one element of silver, copper, manganese and rare earth elements in an industrially advantageous manner. A molded body of sulfide and a method for producing the same. Means for Solving the Problems The inventors of the present invention have recently discovered a molded body of a composite sulfide containing a zinc sulfide having a sulfur/zinc ratio close to 1 or containing zinc sulfide by a method of producing a composite sulfide. The present invention can be achieved by forming a sulfide with at least one element of silver, copper, manganese and a rare earth element. That is, the present invention provides the following. 200918461 [1] - a molded body formed from a composite sulfide containing a sulfur/zinc ratio of 〇. 9 or more vulcanized words or sulfides containing at least one element of zinc sulfide and silver, copper I, and rare earth elements. [2] The molded body as described in [丨], wherein the relative density of the molded body is 0. 9 or more. [3] The molded article according to [IU] or [2], wherein the moisture contained in the molded body is 50 ppm or less. [4] The molded article according to any one of [3], wherein the sulfate ion contained in the molded body is 500 ppm or less. [5] A method for producing a molded body composed of a composite sulfide containing zinc sulfide or a sulfide containing at least one element of zinc sulfide and silver, copper, manganese and a rare earth element, characterized in that In order to contain a particle size of 1 〇〇 / / m or less 'in the specific surface area measured 〇. 2m2/g~50 m2/g of zinc sulfide or a composite sulfide containing sulfides of at least one element of zinc sulfide and silver, copper, manganese and rare earth elements, above 700 °C and above 1 00 °C The temperature is subjected to pressure molding. [6] The method for producing a molded article according to [5], wherein the X-ray crystal analysis of the composite sulfide containing zinc sulfide or a sulfide containing at least one element of zinc sulfide and silver, copper, manganese, and a rare earth element In the middle, the half-height of the diffraction peak of 2 0 = 3 3 ° is 0. 2°~1. 5°. [7] The method for producing a molded article according to [5] or [6], wherein the composite sulfide system containing zinc sulfide or a sulfide containing at least one element of zinc sulfide and silver, copper, manganese, and a rare earth element It is prepared under an aqueous solution. 200918461 EFFECT OF THE INVENTION The molded body composite vulcanizate of the present invention contains vulcanized zinc having a sulfur/zinc ratio of @1 or vulcanized with at least one element of zinc sulfide and silver, _, M s # ± element A material which provides zinc sulfide having high moldability which becomes a target at the time of the ruthenium layer. T, m _ § 3 is more concise "Zinc sulphide or a composite sulphide containing at least one element of zinc sulfide and silver, copper, _ & g ± %" """, "sulfide complex" and so on. [Embodiment] The best mode for carrying out the invention In the present invention, it is preferred to contain zinc sulfide or a composite sulfide containing sulfide of at least one element of zinc sulfide and silver, copper, bell and rare earth halogen. It is possible to use a composite sulfide containing zinc sulfide which can be prepared in an aqueous solution or a sulfide containing at least one element of zinc sulfide and silver, copper, a bell and a rare earth element or silver, copper, manganese and a rare earth element. The sulfide of at least one element is mixed with the composite sulfide obtained by zinc sulfide prepared under an aqueous solution. The method of preparing the aqueous solution is not particularly limited. However, in the case of a method of reacting a salt containing zinc with a vulcanizing agent, it is also possible to produce a substance which is either alkaline or acidic. For example, it can be prepared by mixing an aqueous solution of zinc nitrate with an aqueous solution of sodium sulfide at room temperature, adding thioacetamide to an aqueous solution of zinc nitrate, and reacting it at a temperature of about 1 〇〇t to prepare 200918461 For the salt containing zinc to be used in the liquid phase, a halide such as zinc chloride or zinc bromide, zinc sulfate, zinc sulfite zinc phosphate, zinc nitrate or zinc carbonate, or zinc formate can be used. , organic acid salts such as zinc acetate and zinc oxalate. These may be anhydrous salts and may be aqueous salts. These can be used in a single use and mixed. In terms of the purity of the salt to be used, there is no particular limitation. The higher the better, in particular, the use of a metal-free substance such as iron, nickel, cobalt, chromium or tungsten can be used, and the obtained molded body is used for the production of a phosphor. The situation is better. In the case of preparing a composite sulfide in a liquid phase, at least one salt of silver, copper, manganese and a rare earth element is added to a salt containing zinc to prepare a composite sulfide. If necessary, it can act as a precursor to the elements of silver, copper, manganese and rare earth elements as acceptors, so that elements such as aluminum, gallium, indium, chlorine and bromine are present in the liquid phase. The body element needs to be taken from the composite sulfide. As the salt of silver, copper, manganese and a rare earth element and a salt of a donor element, the above-mentioned halogen salt, mineral acid salt or organic acid salt can be used, and these may be anhydrous salts and may be aqueous salts. These can be used in a single use and mixed. There is no particular limitation on the purity of the salt to be used, but the higher the better, especially if a metal impurity containing no iron, nickel, cobalt, chromium, tungsten or the like is used, the obtained molded body is used for the firefly. The case of the manufacture of light bodies is preferred. There is no particular limitation on the amount of the element acting as a donor relative to the silver, copper, manganese and rare earth element elements contained in the composite sulfide and the silver, copper, and rare earth element elements as acceptors, but Too much amount, because of the interaction between 200918461 and the other, the fluorescence yield is lowered, which is not good, and the amount of too little is not good because the amount of fluorescence taken out is lowered. Therefore, it is appropriate to have a range of 50 to 50,000 ppm', preferably 100 to 40,000 ppm, more preferably 300 to 30,000 ppm. As the vulcanizing agent used in the present invention, an alkali metal sulfide such as hydrogen sulfide, lithium sulfide, sodium sulfide or potassium sulfide, or a thioguanamine-thiourea such as thioformamide or thioacetamide may be used. Wait. The amount of these vulcanizing agents used does not need to be different depending on the method of application, and is usually relative to the zinc salt used. The range of 1 to 5 equivalents ' takes into account the formation efficiency and economy of sulfides, and uses 0. 5 to 3 equivalents are preferred, more preferably 0. 8 to 2 equivalents. In the present invention, liquid phase modulation is preferably carried out in water. In order to use the obtained sulfide as a phosphor, it is preferred that the obtained sulfide is not contained. Therefore, the water to be used is preferably ion-exchanged water, and each of heavy metals such as iron, nickel, and cobalt is 50 ppm or less, preferably 10 ppm or less, and each of typical metals such as sodium, potassium, calcium, and magnesium is 500 ppm or less. It is less than l〇〇ppm. In the liquid phase preparation, a metal salt which is used as a particle size adjusting agent such as magnesium sulfate (aggregation effect by an electrolyte) may be present in the liquid phase. Such a metal cannot be extracted from sulfides in the final stage due to washing or the like. The reaction temperature in the liquid phase preparation varies depending on the vulcanizing agent used, and at a too low temperature, the reaction progresses remarkably slowly, which is not preferable, and at an excessively high temperature, the concentration in the hydrogen sulfide solution is lowered due to vulcanization. The efficiency of the agent is lowered, which is not good. It is usually in the range of 5 ° C to 120 ° C, more preferably 10 ° C to 100 ° C. -10- 200918461 application. The method of the reaction is not particularly limited, and any one of a batch type and a continuous type may be employed. The sulfide obtained in the liquid phase preparation can be separated from water by decantation or centrifugation, and washed with ion-exchanged water, and washed to adjust the pH of the water-washed layer to 6 to 8. The washed sulfide may be removed by vacuum drying or hot air drying at a temperature below 150 ° C, and dried. In terms of drying time, it is needless to say that it depends on the amount of water contained, and is usually from 1 hour to 50 hours, and in consideration of the efficiency of drying, it can be 1. It is implemented in the range of 5 hours to 20 hours. In the present invention, the moisture content of the obtained molded body is preferably 50 ppm or less. When the amount of water is large, it is not preferable because it is used for sputtering or the like because the metal sulfide is oxidized. Therefore, it is preferably from 1 to 30 ppm, more preferably from 1 to 20 ppm. Therefore, the moisture in the sulfide composite at the time of completion of drying (before press molding) is in the range of 1 ppm to 2000 ppm, more preferably 10 to 1000 ppm. The concentration of the sulfate ion contained in the molded article obtained by the present invention is preferably 500 ppm or less. When the amount of sulfate ions is large, in the case of sputtering or the like, the metal sulfide is oxidized or mixed in the film, which is not preferable because of corrosion or decomposition. Therefore, the concentration of the sulfate ion in the molded body is in the range of 1 to 200 ppm, more preferably in the range of 1 to 100 pprn. Therefore, in the range of 1 ppm to 2000 ppm of the sulfate ion concentration in the sulfide composite at the time of completion of the drying (before press molding), the sulfate ion concentration is in the range of 1 to 600 ppm for the purpose of stabilization. The range is better. 200918461 In the case of adding at least one metal of silver, copper, manganese and rare earth elements to zinc sulfide to prepare mixed sulfides, various metal sulfides can be used. These may be used singly or in combination. There is no particular limitation on the purity of the sulfide to be used, but the higher the better, especially when using metal impurities such as iron, nickel, cobalt, chromium, tungsten, etc., the obtained molded body is used for fluorescence. The situation of the manufacture of the body is better. The specific surface area of the obtained sulfide is 0. 2 m2/g to 50 m2/g is preferred. When the specific surface area is too small, sufficient sulfur vapor pressure cannot be generated when fusing is formed during molding, and it is necessary to form a high temperature or a long time because it cannot be bonded, and as a result, the sulfur component may fall off or cause a defect. Not good. In addition, when the surface area is too wide, the temperature rises during molding, and the sulfur vapor pressure rises significantly, and the temperature at which adhesion is impossible is not obtained. Therefore, the sulfur deficiency occurs before the set temperature is reached. It is not good for causing sulfur deficiency. Further, the obtained sulfide was analyzed by X-ray crystal analysis, and the half-height width of the signal 观测 observed using 20 = 3 3° was 0. 2°~1. The object within the range of 5° is further preferred. At 0. When the temperature is 2 or less, the crystallinity is too high, and the formability due to heating/pressurization is deteriorated, which is not preferable. Also, more than one. When the temperature is 5 °, the crystallinity is too low. When the sintering is carried out, decomposition or the like is formed, and the treatment for improving the crystallinity is necessary. In the present invention, the obtained sulfide can be calcined by heating as needed. By this firing, the moisture contained in the composite sulfide can be removed or the decomposition of sulfate ions can be promoted. -12- 200918461 On the one hand, the degree of crystallization of sulfides can be raised, and the specific surface area is significantly reduced, which is necessary for crystallization. Also, when it is too low, it is impossible to complicate only the steps. The temperature of the heating is of course not particularly specific, and is usually carried out in the range of 20 CTC, preferably 300 ° C to 600 ° C. The time of firing is not particularly limited, and the target is 0. The range of 5 to 10 hours can be implemented in the range of 1 to 8 hours in consideration of the device. Usually, it is a matter of course in the case of firing in a reducing atmosphere. In terms of methods, any method of the continuation method is fine. In the atmosphere of the present invention, the atmosphere of the firing is not particularly limited because it causes oxidation of the surface of the composite sulfide, or is carried out under a reducing atmosphere. In the reducing atmosphere, it is possible to add sulfur to the composite sulfide to carry out the firing structure, but considering safety, it is preferable to use the composite sulfur. Thereby, the removal efficiency of the composite sulfate ion can be further improved. The amount of sulfur added during firing is not particularly limited, and 100 parts by weight of the sulfide may be added. 1 to 20 weight machine stability, 0 · 2 to 15 parts by weight, more preferably ί, in the method of adding, solids are mixed with a solvent such as carbon disulfide, and mixed with the composite sulfide is necessary, and Can not be press-formed to obtain the effect of heating, depending on the range of liquid phase modulation - 800 °C, but the heating, cooling capacity, usually in an inert atmosphere or can be batch or separate However, oxygen is present, and in the case of an inert gas atmosphere, hydrogen sulfide is deposited. The sulfur may be added to the sulphide due to the addition of sulfur to the compound of the firing furnace or, generally, relative to the composite, considering operability, i 〇. 3 to 1 〇 by weight. It is also possible to dissolve the sulfur and dry it. -13- 200918461 Furthermore, in the present invention, it is also possible to carry out the baking under vacuum. The temperature at which the treatment is carried out under vacuum is not particularly limited. At an excessively high temperature, the evaporation of the added sulfur may be promoted, or the sulfur of the surface of the composite sulfide may be poor, usually at 100 to 400°. The range of C is more preferably carried out in the range of 100 ° C to 300 ° C. Thereby, oxygen and moisture adhering to the composite sulfide can be effectively removed, and the increase in sulfate ions due to oxidation during firing can be suppressed. The degree of pressure reduction is not particularly limited, and is usually carried out in the range of 1 to 6 QKPa. The obtained fired product can be pulverized and classified as needed, used for molding, and can be washed with acid, ion-exchanged water or the like as needed, and the oxide formed on the surface can be removed. In the case of such washing, it is possible to dry again by vacuum or hot air. In the present invention, before the molding, in order to increase the fluidity and compressibility at the time of the sulfide formation, the powder becomes a powder. In terms of the particle size of the powder, the range of fluidity at the time of molding is preferably maintained, and is usually 1 000 // m or less, more preferably 70 // m or less, in consideration of the load on the molding machine, 50 // Below m, especially below 40 #m is preferred. The method of pulverization is not particularly limited, and a method of pulverizing by a crucible, a ball mill, a turbo honing machine, a cyclone honing machine, or the like can be used. In the present invention, the obtained sulfide is placed in a hot press forming type (mold) and molded by pressure and temperature. In the present invention, any method such as a hot press method or a discharge sintering method may be used for the method of heating and press molding. Carbon, alumina, and Sailong -14-200918461 (sialon) can be used for the material of the hot-pressed forming type. In particular, in the case where the reaction with sulfide is remarkable, it is also possible to use a non-reactant such as glass through a coating film on a surface such as a dragon or a carbon. In the present invention, the pressure for pressurization at the time of hot press forming is not particularly limited, and the molded body is formed by pressurizing at a relative density of 100 kg/cm 2 to 500 kg/cm 2 . Too low a pressure is not good because it cannot increase the relative density. Excessive pressure is not good because it will damage the particle strength. In the present invention, the temperature at the time of hot press forming can be carried out in the range of 600 ° C to 1 00 ° C. At too low a temperature, the adhesion of the particles is not good, and the crystallization of the particles is large at the temperature of the over-tube, which is undesirable because of the occurrence of voids in the formed body. Therefore, it is carried out in the range of 700 ° C to 1050 ° C, more preferably in the range of 800 ° C to 1000 ° C. In the present invention, the order of molding is not particularly limited. For example, if a sulfide is added to the mold, sulfur may be added as needed, and the forming jig may be attached, and the pressure may be reduced to about 140 Pa at a time. The reduced pressure is opened by argon, and this operation is repeated to remove oxygen contained in the sulfide composite and moisture adhering to the surface of the sulfide composite. Next, the mechanical pressure is started in a state where the sulfide is placed under reduced pressure, and the set mechanical pressure (press pressure) is maintained for about 1 minute to about 1 hour when applied to the sulfide. Therefore, the pressure reduction with respect to the sulfide is opened by argon, and the temperature rise is started in a state where the press pressure is applied to the sulfide. At the set temperature, after maintaining the temperature for 1 minute to 1 hour, the temperature is lowered. At the stage of returning to the room temperature, the pressure of the press is released, and the desired molded body can be obtained. -15- 200918461 The method of opening the reduced pressure after the temperature rises, It is also possible to use a method of releasing the pressure of the press and cooling it when the temperature is lowered. After the obtained molded body is detached from the mold, it can be easily used as a target for sputtering by performing honing or the like as needed. The present invention will be described in detail by way of the following examples, but the invention is not limited to the following examples. Example 1 Take zinc nitrate hexahydrate 232. 2g, magnesium sulfate 4. 5g, copper nitrate trihydrate 1. 39g, gallium nitrate octahydrate 3. 35 g of the separable flask was placed in 2 L, and 750 g of ion-exchanged water was added and dissolved. To this, l_5 g of nitric acid was added, and the pH in the system was adjusted to about 2, and a stirrer, a thermometer, and a reflux tube were attached to the flask, and the pH-adjusted liquid was stirred while raising the temperature to 90 °C. When the set temperature is reached, solid thiourea is added. 5 g. After the completion of the addition, after stirring for 2 hours, the system was cooled to 30 ° C in order to stop the reaction. During cooling, a stream of nitrogen is passed through to vent the hydrogen sulfide in the system. The reaction liquid obtained by the reaction was removed by decantation, and the residual solid was washed with ion-exchanged water, and washed to make the pH of the washing liquid about 6. The solid which has been washed is dried by air drying at 15 °C for 12 hours, and vacuum-dried at 120 ° C to obtain a zinc sulfide composite doped with copper. 5g. The obtained zinc sulfide composite system had a particle diameter D 5 0 (center particle diameter) of 1 2 // m. In this particle size distribution, LA-95 0 manufactured by Horiba, Ltd. was used, and the sub-marketing woman was used in a water solvent and measured. The obtained powder was measured by specific surface area measurement by nitrogen adsorption using a Japanese B e 11 company g BELSORP18, and was 4 〇 / -16 - 200918461 m 2 /g. The obtained powder was further measured by XRD, and the half width and width of the shell [] 2 0 = 33 ° was 1. 273. . The water content was measured by a Karl Fischer moisture meter (manufactured by Mitsubishi Chemical Corporation: Type VA-06), and the obtained water content was 892 ppm °. The sulfate ion analysis system was an ion chromatography (ion chromatography) method ( It is implemented by Shimadzu Corporation: type HIC-SP). Dissolve 20mg sample in 5. After 0 g of hydrochloric acid was completely dissolved, the hydrochloric acid was volatilized by a nitrogen gas, and ion-exchanged water was added to become 10. 0g. The amount of sulfate ion detected was 5 62 ppm. 12 g of the obtained zinc sulfide composite was placed in a 30 mm crucible mold and filled in a hot press. The inside of the mold was depressurized to 1 1300 P a ' for 1 Torr, and the reduced pressure was opened with argon at normal pressure. This operation was carried out three times, and the pressure reduction in the mold was opened at normal pressure with argon gas, and the press pressure (200 kg/cm 2 ) was applied to the zinc sulfide composite while raising the temperature to 900 ° C over 1 hour. After the temperature was raised, the press pressure was released and the temperature was cooled to room temperature in 2 hours. The molded body was disengaged from the mold to obtain 3 0 m m Φ and a thickness of 5. 49mm cylindrical target. A portion of the obtained target was collected, dissolved in 1 N hydrochloric acid, and titrated with ethylenediaminetetraacetic acid (EDTA) solution to quantify the metal content. The quantitative result is sulfur/zinc = 〇 · 9 7. The bulk density of the resulting target is 3 · 8 8 g / c m3, relative density (the ratio of bulk density to theoretical density. The theoretical density is the original density of zinc sulfide. 0g/cm3) is 0. 97. The moisture content was 41 ppm and the sulfate ion amount was 22 ppm. Example 2 -17- 200918461 30 g of sulfur-doped copper-doped zinc sulfide obtained in Example 1 was added with 6 g of sulfur, and the mixture was heated at 50 (TC) for 3 hours under nitrogen, and cooled to room temperature. The zinc sulfide composite system has a particle diameter D 5 0 of 1 8 vm. The obtained powder has a specific surface area measured to be 0 · 6 5 m 2 /g. The obtained powder is determined by XRD, then 20 = 33. Height and width are 0. 415. . Further, the water content was 128 ppm and the sulfate ion amount was 255 ppm. 12 g of the obtained zinc sulfide composite was placed in a mold of 30 ηηηηΦ, charged, and placed in a hot press. The pressure was reduced to 130 Pa in the mold for 10 minutes, and the use was opened to normal pressure. These operations were carried out three times, the reduced pressure in the mold was opened to normal pressure with argon gas, and the press pressure (200 Kg/cm 2 ) was applied to the zinc sulfide composite to raise the temperature to 900 ° C for 1 hour. After the temperature was raised, the press pressure was released and the temperature was cooled to room temperature in 2 hours. The molded body was unzipped from the mold to obtain 30 ιηιηΦ and a thickness of 5. 37mm cylindrical target. One part of the obtained target was dissolved in 1 N hydrochloric acid and titrated with EDTA solution. The result of quantitative metal content was sulfur/zinc = 〇. 9 5. The volume density of the obtained ¥ bar is 3. 75g/cm3, relative density (ratio of bulk density to theoretical density) is 0. 95. Further, the amount of water was 49 ppm, and the amount of sulfate ions was 41 ppm. [Example 3] In Example 2, the same as Example 2 except that it was fired at 800 °C. The obtained sulfided complex had a powder having a diameter D50 of 28/zm. The measured surface area of the obtained powder was 〇. 2 2 m2 / g. The obtained powder was subjected to XRD measurement, and the half width and width of 2 0 = 33° were 0. 3 7 5°. Further, the amount of water was 118 ppm, and the amount of sulfate ion was 221 ppm. -18- 200918461 12 g of the obtained zinc sulfide composite was placed in a mold of 30 ηηηηΦ and charged in a hot press. The inside of the mold was depressurized to 13 OPa for 10 minutes, and argon was used to open to normal pressure. This operation was carried out three times, the pressure reduction in the mold was opened by argon gas, and the press pressure (200 Kg/cm 2 ) was applied to the zinc sulfide composite while raising the temperature for 1 hour to 900 °C. After the temperature was raised, the press pressure was released and the temperature was cooled to room temperature in 2 hours. The molded body is detached from the mold to obtain 30 mm0>; thickness 5. 20 mm round cylindrical target. One part of the obtained target was dissolved in 1 N hydrochloric acid, and dissolved in EDTA to determine the metal content. The result was sulfur/zinc=0. 92. The resulting target has a volume density of 3. 73g/cm3, relative density (ratio of bulk density to theoretical density) is 0. 94. Further, the amount of water was 33 ppm, and the amount of sulfate ions was 51 ppm. Example 4 In addition to the first embodiment, the metal salt was only zinc nitrate hexahydrate 2 3 . Other than 2g, the same as in the first embodiment, the zinc sulfide was obtained. 1g. The obtained zinc sulfide was a powder having a particle diameter D50 of 16 // m. The obtained powder was determined to have a specific surface area of 40. 3 m2 / g. The obtained powder was subjected to X RD measurement, and the half width and width of 2 0 = 3 3 ° was 1. 3 7 1 °. Further, the moisture content was 994 ppm and the sulfate ion was 557 ppm. Manganese sulfide 0.05 g of 20 g of the zinc sulfide powder obtained above was mixed and 2,000-times rotation was carried out using a mixer ARE-250 manufactured by Thinky Co., Ltd., and mixing was carried out for 30 seconds. 12 g of the obtained zinc sulfide mixture was placed in a mold of 30 mm Φ and charged to a hot press. The inside of the mold was depressurized to 130 Pa for 1 minute, and placed at atmospheric pressure with argon -19-200918461. This operation was carried out three times, the pressure reduction in the mold was opened to normal pressure with argon gas, and the press pressure (200 kg/cm 2 ) was applied to the zinc sulfide composite while raising the temperature to 900 ° C over 1 hour. After the temperature was raised, the press pressure was released and cooled to room temperature in 2 hours. The molded body is detached from the mold to obtain 30 mm Φ and a thickness of 5. 26mm round cylindrical target. One part of the obtained target was dissolved in 1N hydrochloric acid, titrated with EDTA solution, and the metal content was quantified, and the result was sulfur/zinc=0. 94. The resulting target has a bulk density of 3. 72 g/cm3, relative density (ratio of bulk density to theoretical density) is 0. 93. Further, the amount of water was 27 ppm, and the amount of sulfate ions was 32 ppm. Example 5 6 g of sulfur was added to 30 g of the zinc sulfide mixture obtained in Example 4, and the mixture was heated and calcined at 600 ° C for 3 hours under nitrogen, and cooled to room temperature. The obtained zinc sulfide was a powder having a particle diameter D50 of 32 // m. The measured surface area of the obtained powder is 〇. 221112/2. The obtained powder is subjected to 乂1^ measurement, and the half width and width of 20=33° is 0. 265 °. Further, the amount of water was 1 13 ppm, and the amount of sulfate ion was 245 ppm. The mold into which 12 g of the obtained zinc sulfide was charged was filled in a hot press. The inside of the mold was depressurized to 130 Pa for 10 minutes, and liberated to normal pressure with argon. This operation was carried out three times, the pressure reduction in the mold was opened to normal pressure with argon gas, and the press pressure (200 Kg/cm 2 ) was applied to the zinc sulfide composite while raising the temperature to 900 ° C in one hour. After the temperature was raised, the press pressure was released, and it was cooled to room temperature in 2 hours. The molded body is detached from the mold to obtain 30 η ι η Φ, thickness 5. 15mm round cylindrical target. -20- 200918461 One part of the obtained target was dissolved in IN hydrochloric acid and dissolved in EDTA to quantify the metal content. The result was sulfur/zinc=0. 93. The resulting target has a volume density of 3. 66g/cm3, relative density (ratio of bulk density to theoretical density) is 0. 91. Further, the amount of water was 44 ppm, and the amount of sulfate ions was 57 ppm. [Example 6] In Example 2, except that the zinc sulfide composite was fired at 40 CTC, and the heat molding was carried out at 850 °C, the other was carried out in the same manner as in Example 2. The specific surface area of the obtained zinc sulfide composite powder was determined to be 0. 89 m2/g. The obtained zinc sulfide composite system has a particle diameter D 5 0 of 16 @ m. The obtained powder was subjected to XRD measurement, and the half width and width of 2 0 = 3 3° were 0. 665°. Further, the amount of water was 128 ppm, and the amount of sulfate ions was 255 ppm. One part of the obtained cylindrical IE material was dissolved in 1N hydrochloric acid, titrated with EDTA solution, and the metal content was quantified, and the result was sulfur/zinc. 〇 5. The resulting target has a bulk density of 3. 87g/cm3, relative density (ratio of bulk density to theoretical density) is 0. 96. Further, the water content was 35 ppm and the sulfate ion amount was 55 ppm. [Example 7] In Example 2, except that the zinc sulfide composite was subjected to 70 (rc firing, heat molding was carried out at 750 ° C, the other was carried out in the same manner as in Example 2. The obtained zinc sulfide composite) The specific surface area of the powder is determined by 〇. 丨 8 m2/g. The obtained sulfurized composite system had a particle diameter D 5 0 of 1 9 /z m. The obtained powder was subjected to XRD measurement to be 20 = 33. The half height and width are 〇. 224. . Further, the amount of water was 96 ppm, and the amount of sulfate ions was I38 ppm. -21 - 200918461 One of the obtained cylindrical targets was dissolved in 1N hydrochloric acid and titrated with EDTA solution to quantify the metal content. The result was sulfur/zinc=0. 91. The resulting target has a bulk density of 3. 56g/cm3, relative density (ratio of bulk density to theoretical density) is 0. 89. Further, the amount of water was 21 ppm, and the amount of sulfate ions was 44 ppm. Comparative Example 1 In Example 3, except that sulfur 6 g and sodium chloride were added. 5 g was carried out in the same manner as in Example 3 except that 30 g of the copper-doped zinc-doped zinc sulfide composite obtained in Example 1 was obtained. The obtained zinc sulfide composite system has a particle diameter D50 of 28# m. The obtained powder was measured by specific surface area to be 0. 12 m2/g. The obtained powder was subjected to XRD measurement, and the half width and width of 2 0 = 33° was 〇. 183 °. Further, the amount of water was 88 ppm, and the amount of sulfate ions was 89 ppm. The obtained zinc sulfide composite 12 g was placed in a mold of 30 ηηηηΦ and charged in a hot press. The inside of the mold was depressurized to 130 Pa for 10 minutes, and liberated to normal pressure with argon. This operation was carried out three times, and the pressure in the mold was opened to normal pressure with argon gas, and the press pressure (200 kg/cm2) was applied to the zinc sulfide composite, and the temperature was raised to 900 t in one hour. After the temperature was raised, the press pressure was released and cooled to room temperature in 2 hours. The molded body is detached from the mold to obtain 30 mmCP and a thickness of 4. 92mm round cylindrical target. One part of the obtained target was dissolved in 1 N hydrochloric acid, titrated with EDTA solution, and the metal content was quantified, and the result was sulfur/zinc = 〇. 87. The obtained target has a bulk density of 3. 41 g/cm3, relative density (ratio of bulk density to theoretical density) is 0. 85. Further, the amount of water was 22 ppm, and the amount of sulfate ions was 41 ppm. Comparative Example 2 -22- 200918461 A stirrer, a reflux tube, and a thermometer were placed in a 5-liter three-necked flask to obtain zinc nitrate hexahydrate 149. 1g, copper nitrate trihydrate. 〇 926g, gallium nitrate pentahydrate 〇. 1246 g, 1 liter of ion-exchanged water was added and dissolved to make it under a nitrogen stream. This was added over 20 minutes to make sodium sulfide nonahydrate 145. 5 g of an aqueous solution dissolved in 1 liter of ion-exchanged water. The reaction temperature was 27 ° C and further stirred for 2 hours. The reaction liquid obtained by decantation was removed from the obtained reaction liquid, washed with ion-exchanged water, and washed to adjust the pH of the washing liquid to about 6. The washed solid was dried by hot air at 1 50 ° C for 12 hours to obtain copper-doped zinc sulfide 41 . Lg. The obtained zinc sulfide composite system had a particle diameter D50 of 30 // m. The specific surface area of the obtained powder was determined to be 1 05. 2 m2/g. The obtained powder was subjected to XRD measurement, and the half height and width of 2 Θ = 33° was 2. 22°. Further, the moisture content was 2,450 ppm and the sulfate ion was 1,266 ppm. The obtained zinc sulfide composite 12 g was placed in a mold of 30 ηηηηΦ and charged in a hot press. The inside of the mold was depressurized to 130 Pa for 10 minutes, and argon-decomposed to normal pressure. This operation was carried out three times, and the pressure in the mold was opened to normal pressure with argon gas, and the press pressure (200 Kg/cm 2 ) was applied to the zinc sulfide composite while raising the temperature to 900 ° C for 1 hour. After the temperature was raised, the press pressure was released and the temperature was cooled to room temperature in 2 hours. The molded body is detached from the mold, but is fixed to the mold, and the object cannot be obtained. The moisture content is 899 ppm, and the sulfate ion amount is 4 4 7 ppm. Comparative Example 3 6 g of sulfur is added to the liquid phase-doped copper-doped sulfur-23-200918461 zinc-zinc complex obtained in Example 1, 30 g, The mixture was heated and calcined at 250 ° C for 3 hours under nitrogen, and cooled to room temperature. The obtained zinc sulfide composite system had a particle diameter D 5 0 of 6 2 // m powder. The obtained powder was measured for specific surface area to be 50. 3 3 m2 / g. The obtained powder was subjected to X R D measurement, and the half height and width of 2 0 = 3 3 ° was 1. 8 1 °. Further, the water weight was 1227 ppm and the sulfate ion amount was 723 ppm. 12 g of the obtained zinc sulfide composite was placed in a mold of 30 mm 〇 > and charged in a hot press. The inside of the mold was depressurized to 130 Pa for 10 minutes, and liberated to normal pressure with argon. This operation was carried out three times, and the pressure in the mold was applied to the zinc sulfide composite by argon gas opening to normal pressure 'press pressure (200 kg/cm 2 ), and the temperature was raised to 900 ° C in 1 hour. After the temperature was raised, the press pressure was released, and the temperature was cooled to room temperature in 2 hours. The molded body is detached from the mold, but a part of the molded body is fixed to the wall surface of the mold, and when the target is taken out, peeling occurs from the fixed portion, and the target shape of the target cannot be maintained. The moisture content was 10 1 1 ppm, and the sulfate ion amount was 5 1 2 ppm °. Comparative Example 4 6 g of sulfur and 1.5 g of sodium chloride were added to 3 g of the zinc sulfide mixture obtained in Example 4 and mixed under nitrogen. The mixture was fired at 1 000 ° C for 3 hours and cooled to room temperature. The obtained zinc sulfide composite system had a particle diameter D 5 0 of 3 5 // m powder. The specific surface area of the obtained powder is determined to be 0. 09 m2/g. The obtained powder was subjected to X R D measurement, and the half-height width of 2 β = 3 3 ° was 〇. 1 8 3 °. Further, the water content was 64 ppm and the sulfate ion amount was 66 ppm. The obtained zinc sulfide composite 12 g was placed in a mold of 30 ηηηηΦ and charged in a hot press. The inside of the mold was decompressed to 130 Pa for 10 minutes, and argon was released from -24 to 200918461 to atmospheric pressure. This operation was carried out three times, and the pressure in the mold was opened to normal pressure with argon gas, and the pressure of the press (200 kg/cm 2 ) was applied to the zinc sulfide composite, and the temperature was raised to 900 ° C in one hour. After the temperature was raised, the press pressure was released and the temperature was cooled to room temperature in 2 hours. The molded body was separated from the mold to obtain a cylindrical target having a thickness of 30 mm and a thickness of 3 mm. One part of the obtained target was dissolved in 1 N hydrochloric acid, titrated with E D T A solution, and the metal content was quantified, and the result was sulfur/zinc=0. 86. The obtained target has a bulk density of 3. 41g/cm3, relative density (ratio of bulk density to theoretical density) is 0. 85. Further, the amount of water was 35 ppm, and the amount of sulfate ions was 31 ppm. Comparative Example 5 In Example 2, except that the composite sulfide was fired at 700 ° C, and the heat molding was carried out at 100 ° C, the other was carried out in the same manner as in Example 2. The obtained sulfurized compound system had a particle diameter D50 of 22/m. The obtained powder was measured to have a specific surface area of 0·18 m2/g. The obtained powder was subjected to XRD measurement, and the half width and width of 20 = 33° were 0. 223°. Further, the water content is 96 ppm, and the sulfate ion is 138 ppm. After molding, a part of the cylindrical target is taken, dissolved in 1 N hydrochloric acid, titrated with an EDTA solution, and the metal content is quantified, and the result is sulfur/zinc = 0. 88. The resulting target has a bulk density of 3. 76g/cm3, relative density (ratio of measured density to theoretical density) is 0. 94. Further, the obtained molded body had a water content of I9 ppm and a sulfuric acid ion amount of 37 ppm. Comparative Example 6 - 25 - 200918461 In Comparative Example 4, the same procedure as in Comparative Example 4 was carried out except that the zinc sulfide composite was fired at 1 l ° C. The obtained zinc sulfide composite was a powder having a particle diameter D50 of 38 // m. The specific surface area of the obtained zinc sulfide composite powder was determined to be 0. 08 m2/g. 2 0 = 3 3° half width and width are 0. 144°. Further, the amount of water was 12 ppm, and the amount of sulfate ions was 38 ppm. The obtained zinc sulfide composite 12 g was placed in a mold of 30 ηηηηΦ and charged in a hot press. The inside of the mold was depressurized to 130 Pa for 10 minutes, and liberated to normal pressure with argon. This operation was carried out three times, and the pressure in the mold was opened to normal pressure with argon gas, and the press pressure (200 kg/cm 2 ) was applied to the zinc sulfide composite, and the temperature was raised to 900 ° C in one hour. After the temperature was raised, the press pressure was released, and the temperature was cooled to room temperature in 2 hours. The molded body is detached from the mold to obtain 3〇ΓηιηΦ and a thickness of 4. 35mm round cylindrical target. One part of the obtained target was dissolved in 1 N hydrochloric acid, and the metal content was determined by EDTA solution, and the result was sulfur/zinc=0. 82. The resulting target has a volume density of 3. 07g/cm3, relative density (ratio of bulk density to theoretical density) is 0. 77. Further, the amount of water was I5 ppm, and the amount of sulfate ions was 33 ppm. Example 8 Take zinc nitrate hexahydrate 3 6 0. 0 g, magnesium sulfate 7. 2 g, 0. 1 Μ silver nitrate water solution 57. OmL, gallium nitrate octahydrate 3. 66 g was dissolved in a 2 liter separable flask, and ion exchanged water 丨 2 〇 0 g was added. Add nitric acid to this. 5 g, so that the pH in the system is adjusted to about 2. In this flask, agitator, thermometer, and reflux tube were installed while stirring the pH-adjusted liquid while raising the temperature to 9 (TC. -26-200918461 to the set temperature, then adding thioacetamide 133. 6 g of solid. After the completion of the addition, after stirring for 2 hours, in order to stop the reaction, the inside of the system was cooled to 30 °C. During cooling, a stream of nitrogen gas is introduced to discharge the hydrogen sulfide in the system. The reaction liquid obtained by the reaction was removed by decantation, and the residual solid was washed with ion-exchanged water, and washed to adjust the pH of the washing liquid to 5 or more. The washed solid was dried by hot air at 150 ° C for 12 hours to obtain a silver-doped zinc sulfide composite 93. 5g. The obtained zinc sulfide composite system had a particle diameter D50 of I 6 μm. The obtained powder was subjected to X-ray diffraction (XRD) measurement, and the half-height width of the diffraction peak of 2 Θ = 33° was 1. 363°. Further, the moisture content was 612 ppm and the sulfuric acid ion was 447 ppm. 12 g of the zinc sulfide composite powder obtained above was placed in a mold of 30 ηηηηΦ and charged in a hot press. The inside of the mold was depressurized to 130 Pa for 10 minutes, and the reduced pressure was opened to normal pressure with argon. This operation was carried out three times, and the pressure in the mold was opened to normal pressure with argon gas, and the press pressure (200 Kg/cm 2 ) was applied to the zinc sulfide composite, and the temperature was raised to 900 ° C in 1 hour. After the temperature was raised, the press pressure was released and the temperature was cooled to room temperature in 2 hours. The molded body is detached from the mold to obtain 30 mm Φ and a thickness of 5. 49mm cylindrical target. The obtained target has a bulk density of 3. 89g/cm3, the relative density is 0. 97. One part of the obtained cylindrical target was dissolved in 1 N hydrochloric acid, and titrated with an EDTA solution to quantify the metal content, and the result was sulfur/zinc=0. 92. Further, the amount of water was 24 ppm, and the amount of sulfate ions was 46 ppm. Example 9 In Example 8, the amount of magnesium sulfate used was 2. 5g, the amount of nitric acid used -27- 200918461 is 0. 5 g, the drying temperature of the washed solid was 200 ° C, and the same was carried out as in Example 8, to obtain a silver-doped zinc sulfide composite 9 k 5 g. The obtained zinc sulfide composite system had a particle diameter D 5 0 of 6 7 // m. The half-height width of the diffraction peak of 2 Θ = 33° of the sulphide fresh composite powder is 1. 333. . Further, the water was divided into 506 ppm and the sulfate ion amount was 417 ppm. This powder was pressed in the same manner as in Example 8 to obtain 30 ηηιηΦ and a thickness of 5. 09mm cylindrical coffin. Yield: The volume density of the target is 3. 6 lg/cm3, relative density is 0. 90. One part of the obtained cylindrical target was used, dissolved in 1 N hydrochloric acid, titrated with EDTA solution, and the metal content was quantified, and the result was sulfur/zinc=0. 93. Further, the amount of water was 26 ppm, and the amount of sulfuric acid ions was 48 ppm. Comparative Example 7 In Example 2, except that sodium chloride 1 was added. 5 g and 3 g of magnesium chloride were added to 12 g of the zinc sulfide composite powder, and the mixture was heated and fired at 1100 °C, and the same procedure as in Example 2 was carried out to obtain a zinc sulfide composite after firing. The obtained zinc sulfide composite system had a particle diameter D50 of 104# m. The half-height width of the diffraction peak of 20=33° of the zinc sulfide composite powder is 0. At 198°, the water content was 7 7 ppm and the sulfate ion amount was 67 ppm. This powder was pressed in the same manner as in Example 2 to obtain 30 mm Φ and a thickness of 4. 52mm cylindrical target. The bulk density of the obtained target was 3. 2Og/cm3, relative density is 0. 80. One part of the obtained cylindrical target was dissolved in 1 N hydrochloric acid, titrated with an EDTA solution, and the metal content was determined, and the result was sulfur/zinc=0. 88. Further, the amount of water was 21 ppm, and the amount of sulfuric acid ions was 33 ppm. -28- 200918461 [Table 1] Table 1: Experimental data of zinc sulfide or composite sulfide at the completion of drying D50 (/zm) Specific surface area (m2/g) 2 0=33° Half height width (°) Moisture (ppm) Sulfate ion (ppm) Example 1 12 40. twenty one. 273 892 562 Example 2 18 0. 65 0. 415 128 255 Example 3 28 0. 22 0. 375 118 221 Example 4 16 40. 3 1. 371 994 557 Example 5 32 0. 22 0. 265 113 245 Example 6 16 0. 89 0. 665 128 255 Example 7 19 0. 18 0. 224 96 138 Example 8 16 1. 363 612 447 Example 9 67 1. 333 506 417 Comparative Example 1 28 0. 12 0. 183 88 89 Comparative example 2 30 105. twenty two. 22 2450 1266 Comparative Example 3 62 50. 33 1. 81 1227 723 Comparative Example 4 35 0. 09 0. 18 64 66 Comparative Example 5 22 0. 18 0. 223 96 138 Comparative Example 6 38 0. 08 0. 144 12 38 Comparative Example 7 104 0. 198 77 67 -29- 200918461 [Table 2] Table 2: Experimental data of molded bodies Sulfur/zinc Relative density Moisture (ppm) Sulfate ion (ppm) Example 1 0. 97 0. 97 41 22 Example 2 0. 95 0. 95 49 41 Example 3 0. 92 0. 94 33 51 Example 4 0. 94 0. 93 27 32 Example 5 0. 93 0. 91 44 57 Example 6 1. 05 0. 96 35 55 Example 7 0. 91 0. 89 21 44 Example 8 0. 92 0. 97 24 46 Example 9 0. 93 0. 90 26 48 Comparative Example 1 0. 87 0. 8 1 22 41 Comparative Example 2 Unable to get 899 447 Comparative Example 3 Unable to get 1011 512 Comparative Example 4 0. 86 0. 85 35 31 Comparative Example 5 0. 88 0. 94 19 37 Comparative Example 6 0. 82 0. 77 15 33 Comparative Example 7 0. 88 0. 80 21 33 [Industrial Applicability] According to the present invention, there is provided a zinc sulfide containing or having a sulfur/zinc ratio close to 1, or at least one element containing zinc sulfide and silver, copper, manganese and a rare earth element. A molded body of a sulfide, which has a high formability of a composite sulfide. Such a molded body is useful as a target when forming a light-emitting layer. Further, according to the method for producing a molded article of the present invention of -30-200918461, such a molded article can be produced with high productivity, and is industrially useful. [Simple description of the diagram] Μ . j \ \\ [Main component symbol description] Μ .
JWS -31 -JWS -31 -