200812096 九、發明說明： ' 【發明所屬之技術領域】 本發明係一種無晶鑽石能量轉換器，尤其係一種使用 .無晶鑽石以提高能量轉換效率的無晶鑽石能量轉換器。 【先前技術】 一般能量轉換器，如電池、冷卻器等皆屬於其範疇， 而在此先前技術我們以染料敏化太陽能電池為例，闡述目 前能量轉換器所產生的問題。 # 習用染料敏化電池的工作電極可包括兩部分，其係為 導電基片以及塗設有光敏染料層的半導體電極，該半導體 電極係採用奈米晶粒膜，如二氧化鈦等，而該光敏染料層 係塗設在半導體電極面對導電基片的一側表面，該染料為 釕（Ru )金屬錯合有機光敏染料，於導電基片相對於半導 體電極的另側設有另一電極^而於導電基片與半導體電極 之間還設有電解質層。 其工作原理係當染料層吸收光能後，其中的電子會躍 ® 遷至激發態，因半導體電極的導帶能階低於染料的激發 態，故電子能傳輸至半導體電極，隨後「擴散」至導電基 片，且經外迴路產生光電流至另一電極。失去電子的染料 層處於氧化態，此時電解質層中的電解質會補償染料層中 失去的電子，使氧化態的染料層被還原，該電解質為四級 胺基的碘鹽或鋰碘鹽類溶於高極性的有機溶劑當中，此時 處於氧化態的電解質又會從另一電極中接受電子而還原成 基態，此為染料敏化電池的光電流產生過程。 200812096 ‘ 然而，目前的染料敏化電池具有以下缺點： 1·:半導體電極係以陶宪粉末燒結而成，其燒結溫度 呵’而且為了增加染料的吸附面積，該陶瓷粉末須 使用奈米級的粉末，而且就算粉末為奈米粉末，其 燒結溫度也需達攝氏數百度以上，如奈米二氧化鈦 、疋、σ /皿度而約400 C，其燒結溫度大大限制導電基 片的選擇種類。 # 2.上述半導體奈求膜層的光吸收率低，故需塗佈有色 染料以吸收光。 3.上述半導體奈米膜層之電子傳輸效率差，因半導-^米曰中不存在有内在電場，因此電子傳輸方式 為擴散，使得電子遷移率低，故產生的電子會盘失 去電子的電解質產生結合，並降低光電轉換率:、 至該半導體奈米膜層本身不會有光電效應，九 ，電池需要利用染料吸收光，使電子激發到； • *您、’再使電子遷移’故染料的選擇決定染料敏化 太陽能電池效率。 匕 習用能量轉換器的限制报多，而且電子傳輪的效率為 限料導體電極的燒結溫度以及染料種類，因二 能量轉換效率的能量轉換器是目前業界積極研究的課有良好 為此’本發明人著手研究’發現無晶鑽石為良好的半 導體材枓，由於無晶鑽石為碳❹ (—-ukecarbon)，益晶錯石的的類鑽碳 …日日鑕石的鑽石鍵結係 則扭曲且長短不一 > Μ 、 卫八有不寻Ϊ的金屬鍵，故為非晶質 6 200812096 相，這些扭曲的鍵結會形成無晶鑽石内的缺陷能階，使無 晶鑽石的能隙大小可高可低，無—固定值，結果形成如階 梯般的能隙狀態’故電子报容易在無晶鑽石内部由低能階 躍遷至高能pu形成自&電子’目此無晶鑽石同時具有鑽 石的高硬度以及石墨的導電性’ έ欠而成為良好的半導體材 料。 【發明内容】 為解決習用g量轉換器的問題，本發明人經過不斷的 、试與努力，而發現無晶鑽石是可利用的材料，因此發明 此染料敏化電池。 x 本發明之染料敏化電池，其係包括有： 透明導電基片； 導電基板，其在面對導電基片的—側設有無晶鑽石膜； 、，吸附層，其係設置在透明導電基片與無晶鑽石膜之間， 並吸附在無晶鑽石膜上； 染料層，其係設置在透明導電基片與吸附層之間，並 與吸附層連接。 由於無晶鑽石為含有鑽石鍵結（SP3)、扭曲的四面體 •鍵結（D1Storeted Tetrahedral B〇nding)以及石墨鍵二 (SP2)的碳膜層，其性質兼具鑽石穩定性與石墨的導電性， $晶鑽石本身具光電以及熱電效應，在吸熱或照光後會有 包子產生。無晶鑽石可以物理氣相沉積法塗佈，而且因為 土佈的概度低於2〇〇，故幾乎可塗佈於任何材料上，如 孟屬陶尤、塑膠’並能製作成可繞式的能量轉換器，大 7 200812096 大增加此里轉換為'的適用環境，也因為該無晶鑽石塗佈於 導電基板的溫度低，因此利用該無晶鑽石加入染料敏化電 池中，即可改善習用缺點。 又由於無晶鑽石具有熱電效應以及光電效應，且具有 負陰電性的特性（Negative electron affinity)，因此 其導電帶的最低能階比真空還高，故當電子接受熱能或光 能時，電子會形成自由電子而從無晶鑽石表面射出，使無 φ 晶鑽石在極低的電場誘導下即可射出電子，且當溫度升高 時，射出電子的電流密度呈倍數增加，故可利用溫度差異、 高溫或是光子能量使無晶鑽石激發出電子，達到發電效 果。無晶鑽石可以物理氣相沉積法塗設在任何基材之上， 並調整塗佈參數，以控制表面型態、厚度等種種物理性質， 故無晶鑽石可被配置成任何型式的能量轉換器，俾使得具 有無晶鑽石的能量轉換器之能量轉換效率提高。 【實施方式】 • 請參考第一圖所示，本發明係一種無晶鑽石能量轉換 器，其係包括有： 透明導電基片（70)，該透明導電基板（7〇)的材質可 以選擇導電玻璃、透明導電塑谬，如聚乙二醇對笨二甲酸 酯（PET)等； 導電基板（60)，其於面對導電基片（7〇)的一側設有無 晶鑽石膜（10)，該無晶鑽石膜（1〇)係以物理氣相沉積法 塗佈在導電基板（60) ± ’因無晶鑽石膜(1。)可塗設在幾 乎所有材料之上，故導電基板（6〇)可使用金屬、陶瓷或 8 200812096 是導電塑膠，如聚乙二醇對苯二甲酸酯（PET)等材質； 吸附層（20)，其係設置在該導電基片（7〇)與無晶鑽石 膜（10)之間，並吸附在無晶鑽石膜（1〇)上，該吸附層（2〇) 為可鍵結在無晶鑽石膜（10)表面的高分子材料，如θ碳酸丙 烯’或是酯類，如甲基丙烯酸曱酯等；200812096 IX. Description of the invention: 'Technical field to which the invention pertains» The present invention relates to an amorphous diamond energy converter, and more particularly to an amorphous diamond energy converter using an amorphous diamond to improve energy conversion efficiency. [Prior Art] Generally, energy converters such as batteries and coolers belong to the category. In the prior art, we use dye-sensitized solar cells as an example to illustrate the problems caused by current energy converters. # The working electrode of the conventional dye-sensitized battery may comprise two parts, which are a conductive substrate and a semiconductor electrode coated with a photosensitive dye layer, wherein the semiconductor electrode is made of a nanocrystalline film such as titanium dioxide or the like, and the photosensitive dye The layer is coated on a side surface of the semiconductor electrode facing the conductive substrate, the dye is a ruthenium (Ru) metal misaligned organic photosensitive dye, and the other electrode is disposed on the other side of the conductive substrate with respect to the semiconductor electrode. An electrolyte layer is further disposed between the conductive substrate and the semiconductor electrode. The working principle is that when the dye layer absorbs light energy, the electrons in it will move to the excited state. Since the conduction band energy of the semiconductor electrode is lower than the excited state of the dye, the electrons can be transferred to the semiconductor electrode and then "diffuse". To the conductive substrate, and the photocurrent is generated to the other electrode via the outer loop. The dye layer that loses electrons is in an oxidized state, at which time the electrolyte in the electrolyte layer compensates for the lost electrons in the dye layer, and the dye layer in the oxidized state is reduced. The electrolyte is a quaternary amine-based iodide salt or lithium iodide salt. Among the highly polar organic solvents, the electrolyte in the oxidized state at this time receives electrons from the other electrode and is reduced to the ground state, which is a photocurrent generation process of the dye-sensitized battery. 200812096 ' However, the current dye-sensitized battery has the following disadvantages: 1: The semiconductor electrode is sintered with Taoxian powder, and its sintering temperature is 'and the ceramic powder must be nano-scaled in order to increase the adsorption area of the dye. Powder, and even if the powder is a nano powder, the sintering temperature needs to reach several hundred degrees Celsius or more, such as nano titanium dioxide, tantalum, σ / dish and about 400 C, and the sintering temperature greatly limits the selection of the conductive substrate. # 2. The above semiconductor film has a low light absorptivity, so it is necessary to apply a colored dye to absorb light. 3. The electron transport efficiency of the above semiconductor nanolayer is poor, because there is no intrinsic electric field in the semiconducting-methane, so the electron transport is diffused, so that the electron mobility is low, so the generated electrons lose electrons. The electrolyte produces a combination and reduces the photoelectric conversion rate: until the semiconductor nanofilm layer itself does not have a photoelectric effect, the battery needs to absorb light by the dye to excite the electron; • *, 're-electromigration' The choice of dye determines the efficiency of the dye-sensitized solar cell. There are many restrictions on the use of energy converters, and the efficiency of the electron transfer wheel is the sintering temperature of the limiting conductor electrode and the type of dye. The energy converter of the two energy conversion efficiency is currently actively studied in the industry. The inventors set out to study 'the discovery of crystallization-free diamonds as good semiconductor materials, because the crystallization of diamonds is carbon ❹ (-- ukecarbon), the diamond-like carbon of Yijing shale... The diamond bond system of the Japanese ochre is distorted And the length is different. Μ, 卫八 has a metal bond that is not looking for, so it is amorphous 6 200812096 phase, these twisted bonds will form the defect level in the crystallization diamond, making the gap of the amorphous diamond The size can be high or low, no-fixed value, and the result is a step-like energy gap state. Therefore, the electronic newspaper easily transitions from a low-energy step to a high-energy pu inside the amorphous diamond to form a self-purity diamond. The high hardness of diamonds and the electrical conductivity of graphite are a good semiconductor material. SUMMARY OF THE INVENTION In order to solve the problem of the conventional g-quantity converter, the inventors have found that a crystal-free diamond is a usable material through continuous trial and effort, and thus the dye-sensitized battery is invented. The dye-sensitized battery of the present invention comprises: a transparent conductive substrate; a conductive substrate provided with an amorphous diamond film on a side facing the conductive substrate; and an adsorption layer disposed on the transparent conductive substrate Between the sheet and the amorphous diamond film, and adsorbed on the amorphous diamond film; the dye layer is disposed between the transparent conductive substrate and the adsorption layer, and is connected to the adsorption layer. Since the amorphous diamond is a carbon film layer containing diamond bond (SP3), twisted tetrahedral bond (D1Storeted Tetrahedral B〇nding) and graphite bond II (SP2), its properties are both diamond stability and graphite conductivity. Sex, the crystal diamond itself has photoelectric and thermoelectric effects, and there will be buns after heat absorption or illumination. Amorphous diamonds can be coated by physical vapor deposition, and because the soil cloth is less than 2 inches, it can be applied to almost any material, such as Meng Tao, plastic, and can be made into a wrapable type. The energy converter, Big 7 200812096 greatly increases the applicable environment for conversion to ', and because the amorphous diamond is applied to the conductive substrate at a low temperature, it can be improved by adding the amorphous diamond to the dye-sensitized battery. Conventional shortcomings. Since the amorphous diamond has a thermoelectric effect and a photoelectric effect, and has a negative electron affinity, the lowest energy level of the conductive strip is higher than the vacuum, so when the electron receives heat or light, the electron Free electrons are formed and emitted from the surface of the amorphous diamond, so that the φ-free crystal can emit electrons under the induction of an extremely low electric field, and when the temperature rises, the current density of the emitted electrons increases exponentially, so the temperature difference can be utilized. High temperature or photon energy causes the crystalless diamond to excite electrons to achieve power generation. Amorphous diamonds can be applied to any substrate by physical vapor deposition, and the coating parameters can be adjusted to control various physical properties such as surface morphology and thickness. Therefore, amorphous diamonds can be configured into any type of energy converter. , 俾 makes the energy conversion efficiency of the energy converter with amorphous diamond increased. [Embodiment] Please refer to the first figure, the present invention is an amorphous diamond energy converter, which comprises: a transparent conductive substrate (70), the transparent conductive substrate (7 〇) material can be selected to be electrically conductive Glass, transparent conductive plastic, such as polyethylene glycol to dimethacrylate (PET), etc.; conductive substrate (60), which is provided with an amorphous diamond film on the side facing the conductive substrate (7〇) (10) The amorphous diamond film (1〇) is coated on the conductive substrate by a physical vapor deposition method (60) ± 'Since the amorphous diamond film (1.) can be coated on almost all materials, the conductive substrate (6〇) can use metal, ceramic or 8 200812096 is a conductive plastic, such as polyethylene terephthalate (PET) and other materials; adsorption layer (20), which is set on the conductive substrate (7〇 Between the amorphous diamond film (10) and the amorphous diamond film (1〇), the adsorption layer (2〇) is a polymer material that can be bonded to the surface of the amorphous diamond film (10). Such as θ propylene carbonate 'or esters, such as methacrylate methacrylate;
染料層（30)，其係設置在該導電基片（7〇)與吸附層（2〇) 之間，並連結於吸附層（20)，俾使得該吸附層（2〇) 一端 吸附考無晶鑽石膜（i 〇 )、另一端連結著染料層（⑷之 染料分子，該染料層（30 )係作為光敏化劑之用，其由單 層或是多層染料分子的有機光敏染料，該有機光敏染料為 聯吡啶釕染料或紅汞； 封裝體（50)，其係設置在該吸附層（2 兩側’以將吸附層(20)與染料層⑽固定於導； 與導電基板⑽）之間，該封裝體（5())係絕緣體，且可為 如熱熔膠、塑膠等的彈性材料，使該無晶鑽石能量轉換哭 成為具有彈性、可彎曲的可繞式能量轉換器； 吃解液層(40) ’其係设置在染料層(3〇)與導電基片（7〇) 之::，以幫助電子傳遞’該電解液層（4〇)為氧化還原電 解貝溶液，可選用蛾離子電解質溶液，也可添加固化劑以 固化電解質，以避免電解溶液有流出該電池的疑慮。 由於無晶鑽石係略親油，〖生’因此當上述染料層為油性 染料分子，如尼羅红（·〗 (ΜΗ『Μ)時，則設置在無晶鑽石膜 ^料層之間以將染料層固定於無晶鑽石膜的吸附層則可 以省略。 9 200812096 實施例 為使為使熟知該項技術人士可確實了解本案之可行 性，故下列實驗及其結果分別證明無晶鑽石具光電、熱電 效應，吸收光子能量與熱能後產生電壓、電流的結果，以 證明利用無晶鑽石能量轉換器具有良好的能量轉換效率。 實施例1. 請參考第二圖所示，其係無晶鑽石在真空以及不同外 壓偏壓的環境下，吸收熱能以及吸收光能後所產生之電流 密度的比較圖，其顯示出光能可大大激發無晶鑽石的電 子，而且電流密度也會隨著溫度而上升，當施加的溫度為 1 0 0DC時，無晶鑽石電流密度約為施加溫度在54°C時的1. 6 倍（電場為3ν/μιη );由此可得知本發明之無晶鑽石能量 轉換器具明顯的光電效應及熱電效應。 實施例2. 請參考第三圖所示，本發明之無晶鑽石能量轉換器對 光照極為敏感，其吸收光能後電壓與電流會瞬間急速上 升，光照結束後電壓電流急速下降。而在光照過程中，電 壓上升後即呈現穩定狀態，且電流隨著時間會不斷上升， 故可證明本發明之無晶鑽石能量轉換器兼具可行性與實用 性。 【圖式簡單說明】 第一圖係本發明之結構示意圖。 10 200812096 第二圖係本發明之無晶鑽石膜在真空以及外壓偏壓的 環境下’吸收熱能以及吸收光能後所產生之電流密度圖。 第二圖係本發明在照光過程中，電壓與電流隨時間的 變化。 、 【主要元件符號說明】 (10)無晶鑽石膜 (2 0 )吸附層 (3 0 )染料層 (40 )電解液層 (5 0 )封裝體 (60)導電基板 (70)透明導電基板a dye layer (30) disposed between the conductive substrate (7〇) and the adsorption layer (2〇) and coupled to the adsorption layer (20), such that the adsorption layer (2〇) is adsorbed at one end a crystal diamond film (i 〇), and a dye layer ((4)) is attached to the other end, and the dye layer (30) is used as a photosensitizer, and the organic photosensitive dye is composed of a single layer or a plurality of dye molecules. The photosensitive dye is a bipyridyl hydrazine dye or red mercury; a package (50) disposed on the adsorption layer (on both sides of '2 to fix the adsorption layer (20) and the dye layer (10) to the conductive; and the conductive substrate (10)) The package (5()) is an insulator, and may be an elastic material such as hot melt adhesive, plastic, etc., so that the amorphous diamond energy is converted into a flexible and bendable wraparound energy converter; The liquid-dissolving layer (40) is disposed on the dye layer (3〇) and the conductive substrate (7〇): to help electron transfer 'the electrolyte layer (4〇) is a redox electrolysis solution, Use a molybdenum ionic electrolyte solution, or add a curing agent to cure the electrolyte to avoid the outflow of the electrolytic solution. The battery is suspected. Since the amorphous diamond is slightly oleophilic, the raw layer is therefore set as the amorphous dye film when the dye layer is an oily dye molecule, such as Nile Red (· Μ (Μ Μ)). The adsorption layer between the layers to fix the dye layer to the amorphous diamond film can be omitted. 9 200812096 The examples are such that the following experiments and their results respectively prove that the person skilled in the art can understand the feasibility of the case. The crystal diamond has photoelectric and thermoelectric effects, and absorbs photon energy and heat energy to produce voltage and current results to prove that the use of the amorphous diamond energy converter has good energy conversion efficiency. Embodiment 1. Please refer to the second figure, A comparison of the absorption of thermal energy and the current density generated by absorbing amorphous light in a vacuum and different externally biased environments, which shows that light energy can greatly excite electrons of crystallization diamonds, and current density The current density of the amorphous diamond is about 1.6 times the application temperature at 54 ° C (the electric field is 3ν / μιη); It is known that the amorphous diamond energy converter of the present invention has obvious photoelectric effect and thermoelectric effect. Embodiment 2. Referring to the third figure, the amorphous diamond energy converter of the present invention is extremely sensitive to light, and the voltage after absorbing light energy The current and the current will rise rapidly and the voltage and current will drop rapidly after the end of the illumination. In the process of illumination, the voltage will rise after the voltage rises, and the current will rise with time, so the amorphous diamond energy converter of the present invention can be proved. The first figure is a schematic diagram of the structure of the present invention. 10 200812096 The second figure is the absorption of thermal energy of the amorphous diamond film of the present invention under vacuum and external pressure bias environment. And the current density map generated after absorbing the light energy. The second figure is the change of voltage and current with time in the illumination process of the present invention. [Description of main component symbols] (10) Amorphous diamond film (20) Adsorption layer (30) Dye layer (40) Electrolyte layer (50) Package (60) Conductive substrate (70) Transparent conductive substrate