TW201348500A - Method of using chemical bonding to form compound epitaxial layer and epitaxial product - Google Patents
Method of using chemical bonding to form compound epitaxial layer and epitaxial product Download PDFInfo
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本發明係關於一種利用化學鍵結形成化合物磊晶層的方法及磊晶產品，主要係在接觸層上形成一不飽和離子鍵結層，並以能量激發的方式在不飽和離子鍵結層的非金屬離子上形成懸空鍵結，並利用懸空鍵結的極性，以化學鍵結的方式，在不飽和離子鍵結層上形成化合物磊晶層，令製造廠商在不需採用昂貴的分子束磊晶技術的情況下，即可製作出品質穩定的鏡面狀平面晶之磊晶層。 The invention relates to a method for forming a compound epitaxial layer by chemical bonding and an epitaxial product, which mainly forms an unsaturated ion bonding layer on the contact layer and is in an energy-excited manner in the non-saturated ion bonding layer. A dangling bond is formed on the metal ion, and the epitaxial layer of the compound is formed on the unsaturated ion bonding layer by chemical bonding using the polarity of the dangling bond, so that the manufacturer does not need to use expensive molecular beam epitaxy technology. In this case, an epitaxial layer of a mirror-like planar crystal of stable quality can be produced.
按，磊晶(Epitaxy)技術是一種應用於半導體元件製造過程中的技術，其目標係在原有晶片上長出新結晶，以製成新半導體層，此種技術又稱為磊晶成長(Epitaxial Growth)，而利用磊晶技術成長出的結晶或晶粒即稱為磊晶。磊晶技術可用以製造矽電晶體及CMOS(Complementary metal-oxide-semiconductor)積體電路等各種元件，且在製作化合物半導體時，磊晶技術更是不可或缺的重要技術。 According to Epitaxy technology, it is a technology applied in the manufacturing process of semiconductor components. Its goal is to grow new crystals on the original wafer to make a new semiconductor layer. This technology is also called epitaxial growth. Growth), and crystals or grains grown by epitaxial technology are called epitaxes. Epitaxial technology can be used to fabricate various components such as germanium transistors and CMOS (Complementary Metal-oxide-semiconductor) integrated circuits, and epitaxial technology is an indispensable technology in the fabrication of compound semiconductors.
磊晶技術包括化學氣相沉積法(Chemical Vapor Deposition，簡稱CVD)、分子束磊晶技術(Molecular Beam Epitaxy，簡稱MBE)、真空蒸鍍技術、液態磊晶技術(Liquid Phase Epitaxy，簡稱LPE)及固相磊晶技術(Solid Phase Epitaxy，簡稱SPE)。在半導體基板上生長一層磊晶，是半導體製程中一項基本且重要的技術，而磊晶的厚度及成分控制，將大幅影響產品的 特性及良率，在各種磊晶技術中能完全達到精度要求者，可能只有分子束磊晶(MBE)，故製造廠商為了生產鏡面狀平面晶之磊晶產品，通常是採用分子束磊晶技術(MBE)，該技術是由貝爾實驗室的J.R.亞瑟(J.R.Arthur)和卓以和(Alfred Y.Cho)所發明。分子束磊晶技術是使單晶材料生長的一種方法，且必須在高真空或超高真空(ultra-high vacuum)的環境進行。 Epitaxial technology includes Chemical Vapor Deposition (CVD), Molecular Beam Epitaxy (MBE), vacuum evaporation technology, Liquid Phase Epitaxy (LPE) and Solid Phase Epitaxy (SPE). The growth of a layer of epitaxial on a semiconductor substrate is a fundamental and important technology in semiconductor manufacturing, and the thickness and composition control of epitaxial wafers will greatly affect the product. Characteristics and yield, in the various epitaxial technology can fully meet the accuracy requirements, may only be molecular beam epitaxy (MBE), so manufacturers in order to produce mirror-like planar crystal epitaxial products, usually using molecular beam epitaxy technology (MBE), the technology was invented by JR Arthur and Alfred Y. Cho from Bell Labs. Molecular beam epitaxy is a method of growing single crystal materials and must be carried out in a high vacuum or ultra-high vacuum environment.
分子束磊晶最重要的重點是其低沉積率，通常使薄膜以每小時低於1000奈米的速度磊晶生長，但低沉積率意味著真空程度必須足夠高，以達到其他沉積方式同等級別的潔淨程度。在固體源的分子束磊晶過程中，元素會以超純(ultra-pure)的形式被獨立加熱，直到其開始緩慢升華為氣態物質，該氣態物質將會在晶圓上凝結，並互相作用，例如以鎵和砷作用產生單晶砷化鎵。之所以稱為「分子束」，是由於過程中的氣體原子並不產生交互作用，且亦不與真空室物質反應。在磊晶過程中，製造廠商可利用反射高能電子繞射來檢測晶體層次生長的進程，並藉由控制反應室的閥門，以精確控制每個晶體生長層次，使其精確度可以達到單層原子。磊晶成長的速率完全由單位時間內射到基板表面的分子數目決定，由於磊晶速度慢，所以可以很精確的控制磊晶層的厚度。 The most important focus of molecular beam epitaxy is its low deposition rate, which usually causes the film to grow at a rate of less than 1000 nm per hour, but the low deposition rate means that the vacuum must be high enough to achieve the same level of other deposition methods. The degree of cleanliness. During molecular beam epitaxy of a solid source, the elements are heated independently in an ultra-pure form until they begin to sublime slowly into a gaseous substance that will condense on the wafer and interact with each other. For example, gallium and arsenic are used to produce single crystal gallium arsenide. The reason why it is called "molecular beam" is because the gas atoms in the process do not interact and do not react with the vacuum chamber material. In the epitaxial process, manufacturers can use reflective high-energy electron diffraction to detect the progress of crystal gradation growth, and by controlling the valve of the reaction chamber, precisely control each crystal growth level to achieve a single layer of atomic precision. . The rate of epitaxial growth is completely determined by the number of molecules that hit the surface of the substrate per unit time. Due to the slow epitaxial speed, the thickness of the epitaxial layer can be precisely controlled.
製造廠商採用分子束磊晶技術(MBE)製成的鏡面狀平面晶之產品，即不會有島狀成核(island type nucleation)或塊狀成長(cluster growth)等柱狀晶的特徵。然而，藉由分子束磊晶技術所產出之產品，由於磊晶層之間係以物理接觸的方式相結合，其結合的強度往往較弱，發明人根據多年的研究與觀察發現， 以習知分子束磊晶技術所製成的產品，往往會有各磊晶層分離剝落的問題發生，相當不理想。再者，分子束磊晶技術常會遭遇到磊晶障壁高的問題，且分子束磊晶的製程成本極高，對於製造廠商而言更是一大負擔。 The manufacturer uses mirror-like planar crystals made by molecular beam epitaxy (MBE), which does not have the characteristics of columnar crystals such as island type nucleation or cluster growth. However, the products produced by the molecular beam epitaxy technology, because of the physical contact between the epitaxial layers, the strength of the combination is often weak, the inventors found based on years of research and observation, Products made by conventional molecular beam epitaxy technology often have the problem of separating and peeling off the epitaxial layers, which is quite unsatisfactory. Furthermore, molecular beam epitaxy often encounters problems with high epitaxial barriers, and the process cost of molecular beam epitaxy is extremely high, which is a big burden for manufacturers.
此外，經查有研發單位研發出一種以氮化鈦作為磊晶緩衝層之三五族AlGaInN氮化合物基板結構(台灣公告第I264835號發明專利)，其係在矽基板表面上，形成一氮化鈦緩衝層。以矽做為三五族氮化合物磊晶基板具有下列幾項優點：(1)可簡化製程及降低成本、(2)優良導熱性、(3)大面積(目前可至12吋以上)、(4)可結合目前以矽為主的半導體技術。不過由於矽之(111)面與三五族AlGaInN氮化合物之(0001)面晶格常數相差甚大，其間之晶格不匹配程度高，因此首先必須先在矽上成長一層緩衝層(buffer layer)，而後再製作元件所需之氮化合物薄膜，以克服晶格不匹配所造成的應力問題。該專利前案是直接以金屬有機化合物化學氣相沉積法，成長出氮化鈦薄膜，但發明人深入研究後發現，在實際生產上，該專利前案的作法很難製造出有效的結晶顆粒，故該專利前案所揭露之方法目前並無法適用在實際製程中。 In addition, a research and development unit has developed a three-five-group AlGaInN nitrogen compound substrate structure using titanium nitride as an epitaxial buffer layer (Invention Patent No. I264835), which forms a nitride on the surface of the tantalum substrate. Titanium buffer layer. The use of antimony as a tri-five nitrogen compound epitaxial substrate has the following advantages: (1) simplification of process and cost reduction, (2) excellent thermal conductivity, and (3) large area (currently up to 12 )), ( 4) It can be combined with current semiconductor technology based on germanium. However, since the lattice constant of the (111) plane of the (111) plane and the (0001) plane of the tri-five AlGaInN nitrogen compound is very large, the lattice mismatch between them is high, so first, a buffer layer must be grown on the crucible. Then, a nitrogen compound film required for the component is fabricated to overcome the stress problem caused by lattice mismatch. The predecessor of this patent is to grow a titanium nitride film directly by metal organic chemical chemical vapor deposition. However, the inventors have intensively studied and found that in actual production, it is difficult to produce effective crystalline particles in the practice of the patent. Therefore, the method disclosed in the patent application is currently not applicable to the actual process.
另查，亦有製造廠商開發出一種半導體裝置的製造方法(台灣公告第498564號發明專利)，該方法所製成的產品主要包括基板、鈦層、金屬氮化物層及第Ⅲ族氮化物半導體層，其中該鈦層係形成於基板上，該金屬氮化物層係由選自包括鈦、鋯、鉿及鉭之一種金屬或兩種以上之金屬之氮化物所製成，另，該第Ⅲ族氮化物半導體層係形成於金屬氮化物層上。該專利前案係利用物理氣相沉積的方式，在一鈦層上形成一氮化鈦層(金屬氮化物層)， 惟，發明人研究後發現，物理氣相沉積方式所形成的表面結晶顆粒過小，並無法形成有效用的氮化鈦層，其良率仍無法達到產業上的要求。 In addition, some manufacturers have developed a method for manufacturing a semiconductor device (Taiwan Publication No. 498564), which mainly includes a substrate, a titanium layer, a metal nitride layer, and a Group III nitride semiconductor. a layer, wherein the titanium layer is formed on a substrate, the metal nitride layer being made of a nitride selected from the group consisting of titanium, zirconium, hafnium and tantalum or a metal of two or more kinds, and the third A group nitride semiconductor layer is formed on the metal nitride layer. The patent application uses a physical vapor deposition method to form a titanium nitride layer (metal nitride layer) on a titanium layer. However, the inventors discovered that the surface crystalline particles formed by the physical vapor deposition method are too small to form an effective titanium nitride layer, and the yield thereof cannot meet the industrial requirements.
因此，如何改善習知磊晶技術的諸多問題，以解決傳統物理接觸方式強度不足的缺陷，避免磊晶層分離剝落，令製造廠商不需採用昂貴的分子束磊晶製程，即可製作出鏡面狀平面晶，即為本發明在此欲探討的一重要課題。 Therefore, how to improve the problems of the conventional epitaxial technology to solve the defects of the traditional physical contact method is insufficient to avoid the separation and peeling of the epitaxial layer, so that the manufacturer can produce the mirror-like plane without using the expensive molecular beam epitaxy process. Crystal is an important subject to be explored herein.
有鑑於前揭習知磊晶技術的諸多問題，發明人經過長久努力研究與實驗，終於開發設計出本發明之利用化學鍵結形成化合物磊晶層的方法及磊晶產品，以令製造廠商能在不需採用昂貴的分子束磊晶製程之前提下，利用化學鍵結的方式完成磊晶製程，確保磊晶層間的結合強度，並藉此提升產品的良率。 In view of the many problems of the prior art, the inventors have finally worked hard to study and experiment, and finally developed and designed the method for forming the epitaxial layer of the compound by chemical bonding and the epitaxial product of the present invention, so that the manufacturer can It is lifted before the expensive molecular beam epitaxy process, and the epitaxial process is completed by chemical bonding to ensure the bonding strength between the epitaxial layers and thereby improve the yield of the product.
本發明之一目的，係提供一種利用化學鍵結形成化合物磊晶層的方法，該方法包括：在一基材載板上形成一接觸層；在200℃以上的溫度條件下，使該接觸層表面的原子與非金屬原子產生化學反應，令該非金屬原子形成非金屬離子，並使該非金屬離子以化學鍵結方式與該接觸層表面的原子相互結合，令該非金屬離子在該接觸層表面上形成一不飽和離子鍵結層；以能量激發的方式激發該非金屬離子，使該非金屬離子上尚未與該接觸層表面的原子相互結合的其它鍵結，成為懸空鍵結(dangling bond)；利用化學氣相沉積法，導入有機金屬化合物及反應氣體，令該有機金屬化合物的金屬離子能藉由前述懸空鍵結的電偶極方向導引，均 勻地與該懸空鍵結相結合，並使反應氣體的陰離子以離子鍵結的方式與該金屬離子相結合，以形成化合物磊晶層。藉由本發明之技術特徵，由於該懸空鍵結的極性相當強，且其電偶極吸引力具備明確的方向性，故不僅能降低磊晶障壁，更能導引有機金屬化合物的金屬離子以正確的方向及強勁的鍵結力，與該懸空鍵結均勻地結合，因此，藉由本發明所形成之化合物磊晶層能具備優異的硬度及光譜吸收特性。再者，該化合物磊晶層、該不飽和離子鍵結層及該接觸層之間皆是以化學鍵結的方式相互結合，其鍵結強度遠大於傳統的物理接觸方式，故能有效避免各層分離剝落等問題。另，由於該懸空鍵結的電偶極吸引力能在該化合物磊晶層的形成過程中，引導該金屬離子及陰離子依正確方向排列，故能順利形成鏡面狀平面晶，且不會產生如島狀成核(island type nucleation)或塊狀成長(cluster growth)等柱狀晶的結構特徵，因此，製造廠商不需採用昂貴的分子束磊晶製程，即可製作出鏡面狀平面晶，不僅能節省製程成本，更大幅增加產品的良率。 It is an object of the present invention to provide a method for forming a compound epitaxial layer by chemical bonding, the method comprising: forming a contact layer on a substrate carrier; and forming the contact layer surface at a temperature of 200 ° C or higher The atom reacts with the non-metal atom to form a non-metal ion, and the non-metal ion is chemically bonded to the atom on the surface of the contact layer to form a non-metal ion on the surface of the contact layer. An unsaturated ion-bonding layer; the non-metal ion is excited by energy excitation, and other bonds of the non-metal ion that have not been bonded to atoms on the surface of the contact layer become a dangling bond; a deposition method, introducing an organometallic compound and a reaction gas, so that the metal ion of the organometallic compound can be guided by the electric dipole direction of the dangling bond, The suspension is bonded to the dangling bond, and the anion of the reaction gas is ionically bonded to the metal ion to form a compound epitaxial layer. According to the technical feature of the present invention, since the dangling bond has a relatively strong polarity and the electric dipole attraction has a clear directivity, the epitaxial barrier can be reduced, and the metal ion of the organometallic compound can be guided to be correct. The direction and the strong bonding force are uniformly bonded to the dangling bond, and therefore, the epitaxial layer of the compound formed by the present invention can have excellent hardness and spectral absorption characteristics. Furthermore, the epitaxial layer of the compound, the unsaturated ion-bonding layer and the contact layer are bonded to each other by chemical bonding, and the bonding strength is much larger than the conventional physical contact mode, so that the separation of the layers can be effectively avoided. Peeling and other issues. In addition, since the electric dipole attraction of the dangling bond can guide the metal ions and the anions in the correct direction during the formation of the epitaxial layer of the compound, the mirror-like planar crystal can be smoothly formed without causing The structural characteristics of columnar crystals such as island type nucleation or cluster growth. Therefore, manufacturers do not need expensive molecular beam epitaxy to produce mirror-like planar crystals. It can save process costs and increase the yield of products.
本發明之另一目的，係提供一種利用化學鍵結形成化合物磊晶層的磊晶產品，包括一基材載板、一接觸層及一化合物磊晶層，該接觸層係形成在該基材載板上，其中該接觸層表面的原子能與非金屬原子產生化學反應，令該非金屬原子形成非金屬離子，且該非金屬離子能以化學鍵結方式與該接觸層表面的原子相互結合，而在該接觸層表面上形成一不飽和離子鍵結層，使得該非金屬離子被能量激發後，其上尚未與該接觸層表面的原子相互結合的其它鍵結會成為懸空鍵結，該化合物磊晶層，係利用化學氣相沉積法，導入有機金屬化合物及反應氣體，以令該有機金屬化合 物的金屬離子能藉由前述懸空鍵結的電偶極方向導引，與該懸空鍵結相結合，並使該反應氣體的陰離子以離子鍵結的方式與該金屬離子相結合，而形成在該接觸層上。該化合物磊晶層、該不飽和離子鍵結層及該接觸層之間係以化學鍵結的方式相互結合，故具有強度高之特性，明顯優於習知技術所製成之磊晶產品。 Another object of the present invention is to provide an epitaxial product for forming a compound epitaxial layer by chemical bonding, comprising a substrate carrier, a contact layer and a compound epitaxial layer, the contact layer being formed on the substrate On the plate, wherein the atomic energy of the surface of the contact layer chemically reacts with the non-metal atom, the non-metal atom forms a non-metal ion, and the non-metal ion can bond with the atom of the surface of the contact layer in a chemical bonding manner, and the contact An unsaturated ion bonding layer is formed on the surface of the layer, such that after the non-metal ion is excited by energy, other bonds that have not been bonded to the atoms on the surface of the contact layer become dangling bonds, and the compound is epitaxial layer. Introducing an organometallic compound and a reaction gas by chemical vapor deposition to compound the organometallic compound The metal ion of the object can be guided by the electric dipole direction of the dangling bond, combined with the dangling bond, and the anion of the reactive gas is ionically bonded to the metal ion to form On the contact layer. The epitaxial layer of the compound, the unsaturated ion-bonding layer and the contact layer are chemically bonded to each other, so that the compound has high strength and is superior to the epitaxial product made by the prior art.
本發明之又一目的，乃該基材載板係一矽晶片，而該接觸層為鈦、鉭、鋁、鋅、鈧、鋯或鎂之金屬層，或為硼或矽之兩性元素層。 According to still another object of the present invention, the substrate carrier is a tantalum wafer, and the contact layer is a metal layer of titanium, tantalum, aluminum, zinc, lanthanum, zirconium or magnesium, or an amphoteric element layer of boron or germanium.
本發明之又再一目的，乃該反應氣體可為氨氣(NH3)、磷化氫(PH3)、水(H2O)、硫化氫(H2S)或砷化氫(AsH3)，以製造出含氮、磷、氧、硫或砷元素的化合物磊晶層。 Still another object of the present invention is that the reaction gas may be ammonia (NH 3 ), phosphine (PH 3 ), water (H 2 O), hydrogen sulfide (H 2 S) or arsine (AsH 3 ) ) to produce an epitaxial layer of a compound containing nitrogen, phosphorus, oxygen, sulfur or arsenic.
本發明之又另一目的，乃與該接觸層表面原子產生化學反應的非金屬原子為氮、磷、氧或硫原子。 Still another object of the invention is that the non-metal atom that chemically reacts with the atoms on the surface of the contact layer is a nitrogen, phosphorus, oxygen or sulfur atom.
本發明之再一目的，乃該有機金屬化合物為四(二甲氨基)鈦。 A further object of the invention is that the organometallic compound is tetrakis(dimethylamino)titanium.
為便 貴審查委員能對本發明之目的、結構及其功效，做更進一步之認識與瞭解，茲舉實施例配合圖式，詳細說明如下： For your convenience, the review committee can make a further understanding and understanding of the purpose, structure and efficacy of the present invention. The embodiments are described in conjunction with the drawings, which are described in detail as follows:
發明人在長期從事磊晶技術等相關領域的研發及設計中，發現過去在進行鏡面狀平面晶的磊晶製程時，業者必須採用分子束磊晶技術(MBE)，但分子束磊晶技術的成本相當高，且於磊晶層之間係以物理接觸的方式相結合，其結合力低，往往會有各層分離剝落的問題，導致產品的良率不佳，並不理想。業者雖欲進一步尋求上述問題的改善方案，但尚未獲得完善的解決辦法。有鑑 於此，發明人乃思及藉由懸空鍵結的特性，以化學鍵合的方式，利用一不飽和離子鍵結層連結接觸層及化合物磊晶層，以藉此增加各層之間的結合力，有效避免各層分離剝落等問題。 The inventor has long been engaged in the research and development and design of epitaxial technology and other related fields. It has been found that in the past, in the epitaxial process of mirror-like planar crystal, the industry must adopt molecular beam epitaxy (MBE), but the molecular beam epitaxy technology The cost is quite high, and the epitaxial layers are combined in a physical contact manner, and the bonding strength is low, and there is often a problem that the layers are separated and peeled off, resulting in poor product yield, which is not ideal. Although the industry wants to further seek improvement solutions to the above problems, it has not yet obtained a sound solution. Have a Herein, the inventors thought about bonding the contact layer and the compound epitaxial layer by an unsaturated ion bonding layer in a chemical bonding manner by means of dangling bonding, thereby increasing the bonding force between the layers. Effectively avoid problems such as separation and peeling of each layer.
本發明係一種利用化學鍵結形成化合物磊晶層的方法及磊晶產品，請參閱第1圖所示，以下，茲針對方法及以該方法製成的磊晶產品，提出一較佳實施例進行說明，在本發明之較佳實施例中，該方法係先在一基材載板10上形成一接觸層11，在本較佳實施例中，該基材載板10係一矽晶片，惟，需特別一提的是，該基材載板10的材質並不限於矽晶片，該基材載板10亦可為石英玻璃、銅鉬合金、鎢或鈦等能忍受製程溫度之材質。此外，該接觸層11可為鈦、鉭、鋁、鋅、鈧、鋯或鎂之金屬層，或可為硼或矽之兩性元素層，而在本較佳實施例中，係選用鈦金屬去形成該接觸層11，使鈦金屬與矽晶片作歐姆接觸。所謂歐姆接觸，是指金屬與半導體的接觸，而其接觸面的電阻值遠小於半導體本身的電阻，使得元件操作時，大部分的電壓降在活動區(Active region)而不在接觸面。本發明所選用的基材載板10及接觸層11之材料並不以此為限，凡本技術領域之人士所能輕易思及之變化，均應涵蓋在以下本發明之申請專利範圍內，合先陳明。 The present invention is a method for forming a compound epitaxial layer by chemical bonding and an epitaxial product. Please refer to FIG. 1 . Hereinafter, a preferred embodiment is proposed for the method and the epitaxial product produced by the method. In the preferred embodiment of the present invention, the method first forms a contact layer 11 on a substrate carrier 10. In the preferred embodiment, the substrate carrier 10 is a wafer. It should be particularly noted that the material of the substrate carrier 10 is not limited to the germanium wafer, and the substrate carrier 10 may also be a material that can withstand the process temperature such as quartz glass, copper-molybdenum alloy, tungsten or titanium. In addition, the contact layer 11 may be a metal layer of titanium, tantalum, aluminum, zinc, lanthanum, zirconium or magnesium, or may be an amphoteric element layer of boron or tantalum, and in the preferred embodiment, titanium metal is used. The contact layer 11 is formed such that the titanium metal is in ohmic contact with the tantalum wafer. The so-called ohmic contact refers to the contact of the metal with the semiconductor, and the resistance value of the contact surface is much smaller than the resistance of the semiconductor itself, so that when the component operates, most of the voltage drops in the active region and not on the contact surface. The materials of the substrate carrier 10 and the contact layer 11 used in the present invention are not limited thereto, and any changes that can be easily conceived by those skilled in the art are included in the following patent application scope of the present invention. Heming Chen Ming.
在完成前述接觸層11的形成後，請參閱第2圖所示，在本較佳實施例中，係在200℃以上的溫度條件下，使該接觸層11表面的原子(鈦原子110)與非金屬原子產生化學反應，令該非金屬原子形成非金屬離子120，並使該非金屬離子120以化學鍵結方式與該接觸層11表面的原子相互結合，令該非金屬離子120在該接觸層11表面上形成一不飽和離子鍵結層12。其中，前述非金屬原子 可為氮、磷、氧或硫的原子，而在本較佳實施例中，係選用氮原子作為該非金屬原子，氮原子在與接觸層11表面的原子(鈦原子110)進行化學反應後，即成為氮離子(非金屬離子120)，且形成該不飽和離子鍵結層12。 After the formation of the contact layer 11 is completed, as shown in FIG. 2, in the preferred embodiment, the atoms (titanium atoms 110) on the surface of the contact layer 11 are at a temperature of 200 ° C or higher. The non-metal atom generates a chemical reaction, so that the non-metal atom forms a non-metal ion 120, and the non-metal ion 120 is chemically bonded to the atom on the surface of the contact layer 11, so that the non-metal ion 120 is on the surface of the contact layer 11. An unsaturated ion bonding layer 12 is formed. Wherein the aforementioned non-metal atom It may be an atom of nitrogen, phosphorus, oxygen or sulfur, and in the preferred embodiment, a nitrogen atom is selected as the non-metal atom, and after the nitrogen atom is chemically reacted with an atom (titanium atom 110) on the surface of the contact layer 11, That is, nitrogen ions (non-metal ions 120) are formed, and the unsaturated ion-bonding layer 12 is formed.
請參閱第3圖所示，本發明係以能量激發的方式激發該非金屬離子120，使該非金屬離子120上尚未與該接觸層11表面的原子相互結合的其它鍵結，成為懸空鍵結121。所謂懸空鍵結(dangling bond，亦稱「懸鍵」)，係指未參與鍵結的電子(未成對電子)所佔據之鍵，在本發明中，被激發產生的懸空鍵結121具有極強的活性，且具備一電偶極吸引力。發明人發現，在激發出懸空鍵結121後，能有效降低磊晶障壁，有利於後續磊晶層的形成。在實際製程上，製造廠商可利用雷射作為能量激發的手段，惟，本發明並不以此為限，製造廠商在依本發明之技術特徵進行磊晶製程時，亦可根據實際產品需求及其他製程條件考量，改變能量激發的手段，例如：使用熱能激發或其他方式，凡本發明領域之人士所能思及之轉變，仍屬本發明之等效變化，同樣不脫離本發明之申請專利範圍。 Referring to FIG. 3, the present invention excites the non-metal ions 120 in an energy-exciting manner so that other bonds of the non-metal ions 120 that have not yet bonded to the atoms on the surface of the contact layer 11 become dangling bonds 121. The dangling bond (also referred to as "dangling bond") refers to a bond occupied by electrons (unpaired electrons) that are not involved in the bonding. In the present invention, the dangling bond 121 generated by the excitation is extremely strong. It is active and has an electric dipole attraction. The inventors have found that after the dangling bond 121 is excited, the epitaxial barrier can be effectively reduced, which is favorable for the formation of the subsequent epitaxial layer. In the actual process, the manufacturer can use the laser as a means of energy excitation. However, the present invention is not limited thereto, and the manufacturer may perform the epitaxial process according to the technical features of the present invention, and may also be based on actual product requirements and Other process conditions, such as the use of thermal energy excitation or other means, which can be considered by those skilled in the art, are still equivalent variations of the present invention, and do not depart from the patent application of the present invention. range.
請參閱第4圖所示，在完成前述步驟後，本實施例係利用化學氣相沉積法，導入鈦化合物(有機金屬化合物)及氨氣(反應氣體)，令該鈦化合物的鈦離子130能藉由前述懸空鍵結121的電偶極方向導引，均勻地與該懸空鍵結121相結合，另，請參閱第5圖所示，氨氣(NH3)的氮離子131以離子鍵結的方式與該鈦離子130相結合，以形成氮化鈦磊晶層13(即化合物磊晶層)。本較佳實施例係採用四(二甲氨基)鈦(Tetrakis(dimethylamido) titanium，簡稱TDMAT)作為該有機金屬化合物，並選用氨氣(NH3)作為該反應氣體，四(二甲氨基)鈦係一種有機金屬化合物，惟，該有機金屬化合物並不以四(二甲氨基)鈦為限，製造廠商亦可根據實際製程或產品設計需求，改變該有機金屬化合物的材料，此外，製造廠商亦可採用磷化氫(PH3)、水(H2O)、硫化氫(H2S)或砷化氫(AsH3)，作為該反應氣體，以製造出含磷、氧、硫或砷元素的化合物磊晶層，凡本技術領域之人士所能輕易聯想的材料轉換，仍不脫離本發明之申請專利範圍。 Referring to FIG. 4, after completing the foregoing steps, the present embodiment introduces a titanium compound (organometallic compound) and ammonia gas (reaction gas) by chemical vapor deposition to make the titanium compound 130 of the titanium compound By the electric dipole direction guiding of the dangling bond 121, it is uniformly combined with the dangling bond 121. In addition, as shown in FIG. 5, the nitrogen ion 131 of the ammonia gas (NH 3 ) is ion-bonded. The method is combined with the titanium ion 130 to form a titanium nitride epitaxial layer 13 (ie, a compound epitaxial layer). In the preferred embodiment, Tetrakis (dimethylamido titanium) (TDMAT) is used as the organometallic compound, and ammonia gas (NH 3 ) is selected as the reaction gas, tetrakis (dimethylamino) titanium. An organometallic compound. However, the organometallic compound is not limited to tetrakis(dimethylamino)titanium. The manufacturer may also change the material of the organometallic compound according to the actual process or product design requirements. In addition, the manufacturer also Phosphine (PH 3 ), water (H 2 O), hydrogen sulfide (H 2 S) or arsine (AsH 3 ) may be used as the reaction gas to produce phosphorus, oxygen, sulfur or arsenic. The compound epitaxial layer, which can be easily associated with those skilled in the art, does not depart from the scope of the invention.
藉由本發明之技術特徵，復請參閱第5圖所示，由於該懸空鍵結121的極性相當強，且其電偶極吸引力具備明確的方向性，故不僅能降低磊晶障壁，更能導引鈦化合物的鈦離子130以正確的方向及強勁的鍵結力，與該懸空鍵結121均勻地結合，且能使氮離子131與鈦離子130的結合更加均勻，排列更具一致性，其原因即在於氮離子131與鈦離子130能藉由電偶極，自動調整接觸方向，因此，藉由本發明所形成之氮化鈦磊晶層13不僅品質高，更具備優異的硬度及光譜吸收特性。再者，該氮化鈦磊晶層13、該不飽和離子鍵結層12及該接觸層11之間皆是以化學鍵結的方式相互結合，其鍵結強度遠大於傳統的物理接觸方式，故能有效避免各層分離剝落等問題。不僅如此，本發明不需以傳統方式生長複雜的緩衝層結構，不僅能降低製程成本，減少製程複雜度，更能降低化學品的使用量，達到環保的功效。 According to the technical features of the present invention, as shown in FIG. 5, since the dangling bond 121 has a relatively strong polarity and its electric dipole attraction has a clear directivity, it can not only reduce the epitaxial barrier but also better The titanium ion 130 guiding the titanium compound is uniformly combined with the dangling bond 121 in the correct direction and strong bonding force, and the combination of the nitrogen ion 131 and the titanium ion 130 is more uniform and the alignment is more uniform. The reason is that the nitrogen ions 131 and the titanium ions 130 can automatically adjust the contact direction by the electric dipole. Therefore, the titanium nitride epitaxial layer 13 formed by the present invention is not only high in quality, but also has excellent hardness and spectral absorption. characteristic. Furthermore, the titanium nitride epitaxial layer 13, the unsaturated ion bonding layer 12 and the contact layer 11 are bonded to each other by chemical bonding, and the bonding strength is much larger than the conventional physical contact mode. It can effectively avoid problems such as separation and peeling of each layer. Moreover, the present invention does not need to grow a complicated buffer layer structure in a conventional manner, and can not only reduce the process cost, reduce the process complexity, but also reduce the amount of chemicals used and achieve environmental protection effects.
針對本較佳實施例所製成之產品，發明人以KLA-Tencor公司的量測機台「RS75」，進行四點探針測試時，發現該產品無法被刺穿，經查，探針的材質為碳化鎢，其莫氏硬度為8.5~9.0，由此可 知，根據本發明所製成的磊晶產品具備超硬材料的特徵。此外，發明人更利用THERMA WAVE公司的量測機台「OP2600」，以DUV(Deep ultraviolet，深紫外線)模式進行厚度測試，無法測出正確的厚度，此不僅表示產品的反射率小於13%，更顯示產品在DUV光譜區存在極強的吸收特性。另，發明人利用電子顯微鏡樣本切片厚度檢查(SEM thickness check)，測量出氮化鈦磊晶層13的厚度為30±0.1nm，其均勻度小於0.35%(0.1÷30<0.35%)，符合磊晶製程的產品特性(均勻度小於1.0%)。 For the product made in the preferred embodiment, the inventor used the KLA-Tencor measuring machine "RS75" to perform a four-point probe test, and found that the product could not be pierced, and the probe was examined. The material is tungsten carbide, and its Mohs hardness is 8.5~9.0. It is known that epitaxial products made in accordance with the present invention are characterized by superhard materials. In addition, the inventors used the measurement machine "OP2600" of THERMA WAVE to test the thickness in DUV (Deep Ultraviolet) mode, and the correct thickness could not be measured. This means that the reflectivity of the product is less than 13%. It also shows that the product has strong absorption characteristics in the DUV spectral region. In addition, the inventors measured the thickness of the titanium nitride epitaxial layer 13 by 30±0.1 nm using an electron microscope sample SEM thickness check, and the uniformity thereof was less than 0.35% (0.1÷30<0.35%), which was consistent with Product characteristics of the epitaxial process (uniformity is less than 1.0%).
綜上所述，在本發明中，由於該懸空鍵結121的電偶極吸引力能在該氮化鈦磊晶層13(化合物磊晶層)的形成過程中，引導該鈦離子130(金屬離子)及氮離子131(反應氣體的陰離子)依正確方向排列，故能順利形成鏡面狀平面晶，且不會產生如島狀成核(island type nucleation)或塊狀成長(cluster growth)等柱狀晶的結構特徵，因此，製造廠商不需採用昂貴的分子束磊晶製程，即可製作出鏡面狀平面晶，不僅能節省製程成本，更大幅增加產品的良率。 In summary, in the present invention, since the electric dipole attraction of the dangling bond 121 can guide the titanium ion 130 (metal during the formation of the titanium nitride epitaxial layer 13 (compound epitaxial layer) The ions and the nitrogen ions 131 (the anions of the reaction gas) are arranged in the correct direction, so that the mirror-like planar crystal can be formed smoothly without causing columns such as island type nucleation or cluster growth. The structural characteristics of the crystals, therefore, manufacturers do not need to use expensive molecular beam epitaxy process, can produce mirror-like planar crystal, not only can save process costs, but also greatly increase product yield.
按，以上所述，僅為本發明之較佳實施例，惟本發明之技術特徵並不侷限於此，凡任何熟悉該項技藝者，在本發明之技術領域內，可輕易思及的變化或修飾，皆應涵蓋在以下本發明的申請專利範圍中。 The above description is only a preferred embodiment of the present invention, but the technical features of the present invention are not limited thereto, and any one skilled in the art can easily change in the technical field of the present invention. Or, modifications are intended to be included in the scope of the claims of the invention below.
10‧‧‧基材載板 10‧‧‧Substrate carrier
11‧‧‧接觸層 11‧‧‧Contact layer
110‧‧‧鈦原子 110‧‧‧Titanium atom
12‧‧‧不飽和離子鍵結層 12‧‧‧Unsaturated ion bonding layer
120‧‧‧非金屬離子 120‧‧‧Non-metal ions
121‧‧‧懸空鍵結 121‧‧‧ dangling bonds
13‧‧‧氮化鈦磊晶層 13‧‧‧Titanium nitride epitaxial layer
130‧‧‧鈦離子 130‧‧‧Titanium ions
131‧‧‧氮離子 131‧‧‧Nitrogen ions
第1圖係本發明之較佳實施例之第一示意圖；第2圖係本發明之較佳實施例之第二示意圖； 第3圖係本發明之較佳實施例之第三示意圖；第4圖係本發明之較佳實施例之第四示意圖；及第5圖係本發明之較佳實施例之第五示意圖。 1 is a first schematic view of a preferred embodiment of the present invention; and FIG. 2 is a second schematic view of a preferred embodiment of the present invention; 3 is a third schematic view of a preferred embodiment of the present invention; FIG. 4 is a fourth schematic view of a preferred embodiment of the present invention; and FIG. 5 is a fifth schematic view of a preferred embodiment of the present invention.
10‧‧‧基材載板 10‧‧‧Substrate carrier
11‧‧‧接觸層 11‧‧‧Contact layer
110‧‧‧鈦原子 110‧‧‧Titanium atom
12‧‧‧不飽和離子鍵結層 12‧‧‧Unsaturated ion bonding layer
120‧‧‧非金屬離子 120‧‧‧Non-metal ions
121‧‧‧懸空鍵結 121‧‧‧ dangling bonds
13‧‧‧氮化鈦磊晶層 13‧‧‧Titanium nitride epitaxial layer
130‧‧‧鈦離子 130‧‧‧Titanium ions
131‧‧‧氮離子 131‧‧‧Nitrogen ions
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