TW201703831A - Organic material having a protective layer - Google Patents
Organic material having a protective layer Download PDFInfo
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- TW201703831A TW201703831A TW104124585A TW104124585A TW201703831A TW 201703831 A TW201703831 A TW 201703831A TW 104124585 A TW104124585 A TW 104124585A TW 104124585 A TW104124585 A TW 104124585A TW 201703831 A TW201703831 A TW 201703831A
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本發明涉及一種有機材料,特別是涉及為了實現有機材料的高純度化,利用離子液體對有機材料進行提純,或者在提純後的有機材料的表面塗敷離子液體,從而在有機材料的表面形成保護層。 The present invention relates to an organic material, and more particularly to purifying an organic material by using an ionic liquid in order to achieve high purity of an organic material, or coating an ionic liquid on the surface of the purified organic material to form a surface on the surface of the organic material. Floor.
有機電致發光(EL,electroluminescence)元件為在功函數大且透明的陽極金屬與功函數小的陰極金屬之間由多個薄的有機薄膜層構成,發光原理為若向元件施加正向的電壓,則在陽極電極中,空穴向有機層注入,在陰極中,注入電子,來在發光層重新結合,從而進行發光的顯示器。有機電致發光具有低耗電、寬視角、高速回應速度、廣的驅動溫度範圍等資訊化時代所需的高品質面板特性,此外,有機電致發光元件因製程相對簡單而具有可期待實現超越現有的平板顯示器的低價化的優點。 An organic electroluminescence (EL) element is composed of a plurality of thin organic thin film layers between a large and transparent anode metal and a small work function. The principle of light emission is to apply a positive voltage to the element. In the anode electrode, a hole is injected into the organic layer, and electrons are injected into the cathode to recombine the light-emitting layer to emit a light-emitting display. Organic electroluminescence has high-quality panel characteristics required for information ages such as low power consumption, wide viewing angle, high-speed response speed, and wide driving temperature range. In addition, organic electroluminescent elements can be expected to achieve beyond the relatively simple process. The advantage of the low cost of existing flat panel displays.
有機材料的純度為影響有機電致發光元件的發光特性的因素之一。若在有機材料中混合有雜質,則該雜質 將成為載體的捕集器或成為消光的原因,從而使發光強度及發光效率下降。因此,為了去除雜質,需對有機材料進行提純。 The purity of the organic material is one of the factors that affect the luminescent properties of the organic electroluminescent element. If impurities are mixed in the organic material, the impurities The trap that will become the carrier may cause the extinction, thereby reducing the luminous intensity and the luminous efficiency. Therefore, in order to remove impurities, the organic material needs to be purified.
在對原料進行合成後,有機材料將首先經過利用化學方法的提純製程,這種化學提純製程包括如再結晶(recrystallization)、蒸餾(distillation)及柱色譜(column chromatography)等。若經過這種化學提純製程,可將希望得到的化合物的純度提高至99%以上。 After the synthesis of the raw materials, the organic materials will first undergo a chemical purification process including, for example, recrystallization, distillation, and column chromatography. If this chemical purification process is carried out, the purity of the desired compound can be increased to 99% or more.
作為有機材料的提純方法,通常使用溶劑的再結晶或基於昇華的再結晶。雖然使用溶劑的再結晶具有可對有機材料進行批量提純的優點,但由於使用溶劑,因而具有溶劑容易進入有機結晶中的缺點。即,存在進入有機結晶的溶劑起到雜質的作用,從而降低發光特性的問題。 As a method of purifying an organic material, recrystallization of a solvent or recrystallization based on sublimation is usually used. Although the recrystallization using a solvent has an advantage that the organic material can be subjected to batch purification, since a solvent is used, there is a disadvantage that the solvent easily enters the organic crystal. That is, there is a problem that the solvent that enters the organic crystal acts as an impurity, thereby reducing the luminescent property.
作為其他提純方式,如具有高性能液體色譜(HPLC:High Performance Liquid Chromatography)等色譜方式,在利用如上所述的色譜方式進行提純的情況下,與簡單的化學提純製程相比可實現更高的純度。但實際上這種色譜方式大多僅用於分析,並不適合用於批量生產的材料的提純。 As another purification method, such as high performance liquid chromatography (HPLC: High Performance Liquid Chromatography), in the case of purification by the above-described chromatographic method, it is possible to achieve higher performance than a simple chemical purification process. purity. However, in fact, most of this chromatographic method is only used for analysis, and is not suitable for the purification of materials for mass production.
有機發光材料通常利用昇華提純方法來提純。昇華(sublimate)是指在相平衡度中的三重點以下的溫度和壓力下產生的固體與氣體之間的轉化現象。即使是只要在常壓 下加熱就會被熱分解的物質,也會在三重點以下的低壓狀態下維持不會在較高的溫度下被分解的狀態。利用這種性質,在可控制溫度梯度的昇華裝置內對合成的物質進行加熱來以物質未被分解的狀態與昇華點不同的雜質分離的操作被稱為真空昇華法(vacuum sublimation method)。這種真空昇華法為純物理方法,無需使用輔助試劑或借助其他的化學方法,因而不存在試樣的污染,具有可進行高純度提純的優點,因此,公認為有機電致發光元件用有機材料的提純的有效方法。 Organic luminescent materials are usually purified by sublimation purification. Sublimate refers to the phenomenon of conversion between solids and gases produced at temperatures and pressures below the three points in phase equilibrium. Even as long as it is at atmospheric pressure A substance that is thermally decomposed by heating under a low pressure state below three stresses maintains a state in which it is not decomposed at a higher temperature. With this property, an operation of heating a synthesized substance in a sublimation device capable of controlling a temperature gradient to separate impurities different from a sublimation point in a state in which the substance is not decomposed is referred to as a vacuum sublimation method. The vacuum sublimation method is a purely physical method, and does not require the use of an auxiliary reagent or other chemical methods, so that there is no contamination of the sample, and there is an advantage that high-purity purification can be performed. Therefore, it is recognized as an organic material for an organic electroluminescence element. An effective method of purification.
目前為止,使用最廣泛的有機材料的超高純度提純方式有傾斜加熱式真空昇華提純方法(vacuum train sublimation purification method)。在該方法中,將長管形態的接近真空狀態的腔室分為多個加熱區域,對各加熱區域以從高溫至低溫傾斜的方式進行加熱,從而形成溫度梯度。利用在如上所述的腔室內昇華的材料的昇華點的差異來獲取僅在規定加熱區域析出的材料。通常,在以往的真空昇華提純方法中適用如下製程條件。 Up to now, the ultra-high purity purification method using the most extensive organic materials has a vacuum train sublimation purification method. In this method, a chamber in a near-vacuum state in a long tube form is divided into a plurality of heating regions, and each heating region is heated so as to be inclined from a high temperature to a low temperature to form a temperature gradient. The material precipitated only in the prescribed heating zone is obtained by the difference in the sublimation point of the material sublimated in the chamber as described above. Generally, the following process conditions are applied to the conventional vacuum sublimation purification method.
第一,將加熱區域分為3至9個區域。在所劃分的區域少的情況下,簡單採取高溫、中溫、低溫的方式,在所劃分的區域多的情況下,除了獲取試樣的區域以外,在各區域的溫度梯度範圍內設定加熱溫度。 First, the heating zone is divided into 3 to 9 zones. In the case where the number of divided regions is small, the method of high temperature, medium temperature, and low temperature is simply adopted. In the case where there are many divided regions, the heating temperature is set within the temperature gradient range of each region except for the region where the sample is taken. .
第二,試樣裝載區域設定於真空閥的相反位置。 Second, the sample loading area is set to the opposite position of the vacuum valve.
第三,雖然根據材料的特性而具有偏差,但在流 出載氣之前,腔室的初期壓力為10-2~10-6torr的範圍,並調節用於流出載氣的一側的壓力維持0.1torr至數torr的範圍。載氣使用無反應性的高純度氮氣或氬氣。 Third, although there is a deviation depending on the characteristics of the material, the initial pressure of the chamber is in the range of 10 -2 to 10 -6 torr before the carrier gas is discharged, and the pressure on the side for discharging the carrier gas is maintained at 0.1. Torr to the range of torr. The carrier gas uses unreactive high purity nitrogen or argon.
第四,試樣的裝載以可使載氣移動的方式盡可能不超過管的直徑的1/2。此時,還使用小船形狀的裝載器具。 Fourth, the loading of the sample is such that the carrier gas is moved as much as possible by no more than 1/2 of the diameter of the tube. At this time, a boat-shaped loading device is also used.
在現有的真空昇華提純方法中使用載氣的目的在於,使真空昇華狀態的試樣更好地流動。即,若在接近真空狀態的狀態下沒有載氣,則昇華的試樣分子的流動性差,因而呈現出在過於靠近試樣裝載區域的壁面析出固體粒子的現象。因此,在現有的真空昇華提純製程中,使用載氣成為基本的製程條件。 The purpose of using a carrier gas in the existing vacuum sublimation purification method is to make the sample in a vacuum sublimation state flow better. That is, when there is no carrier gas in a state close to the vacuum state, the fluidity of the sublimated sample molecules is poor, and thus a phenomenon in which solid particles are deposited on the wall surface too close to the sample loading region appears. Therefore, in the existing vacuum sublimation purification process, the use of a carrier gas becomes a basic process condition.
但是,如上所述的現有的真空昇華提純方法存在幾種缺點。現有的真空昇華提純方法的最大問題在於,因載氣導致結有超高純度物質的規定區域被污染。即,存在載氣使裝在用於裝載試樣的區域的原試樣飛散,導致實際形成的超高純度物質所析出的區域受污染的傾向。並且,還引起逐漸向第三區域移動已形成的超高純度物質的析出區域的現象。 However, the existing vacuum sublimation purification method as described above has several disadvantages. The biggest problem with the existing vacuum sublimation purification method is that the prescribed area where ultra-high purity substances are formed due to the carrier gas is contaminated. That is, in the presence of the carrier gas, the original sample contained in the region for loading the sample is scattered, and the region where the ultrahigh-purity substance actually formed is deposited tends to be contaminated. Further, it also causes a phenomenon in which the deposition region of the formed ultrahigh-purity substance is gradually moved to the third region.
載氣不僅在這種製程中起到不利作用,而且在裝載大量試樣的情況下,還對設備產生不利影響,從而引起昇華後的試樣的一部分污染真空泵的現象。即使將用於防止這種現象的捕集裝置設置成高容量結構,也依舊降低真空泵的 性能。 The carrier gas not only plays an adverse role in this process, but also adversely affects the equipment in the case of loading a large number of samples, thereby causing a part of the sublimated sample to contaminate the vacuum pump. Even if the trapping device for preventing this phenomenon is set to a high-capacity structure, the vacuum pump is still lowered. performance.
現有的真空昇華提純方法的其他缺點在於真空通氣(venting)時的飛散現象。在進行真空通氣時,向腔室內送入氮氣,使得壓力成為常壓,在此情況下,有可能產生在腔室內完成提純製程的各試樣之間的飛散現象。這種現象在提純用玻璃管(或水晶管)的兩端全部開放時更加嚴重,因此,經常發生導致已經提純的物質也受污染的事情。 Another disadvantage of the existing vacuum sublimation purification method is the scattering phenomenon during vacuum venting. When vacuum aeration is performed, nitrogen gas is supplied into the chamber so that the pressure becomes a normal pressure, and in this case, scattering between the respective samples in which the purification process is completed in the chamber may occur. This phenomenon is more serious when both ends of the glass tube for purification (or the crystal tube) are opened, and therefore, it is often the case that the substance which has been purified is also contaminated.
綜上所述,昇華提純方法具有利用有機材料的昇華點的差異來將原料物質提純為純度高的有機材料的優點,但也引起了如下的多種問題。 In summary, the sublimation purification method has the advantage of utilizing the difference in sublimation points of the organic materials to purify the raw material into an organic material having a high purity, but also causes various problems as follows.
第一,在提純過程反復執行昇華-逆昇華的過程中,有機物質的相當部分的量與載氣一同作為尾氣來消失,因而與原始物質相比,最終提純物質的收率非常低,而且還發生污染真空泵的問題。 First, in the process of repeated sublimation-sublimation in the purification process, a considerable amount of organic matter disappears together with the carrier gas as the exhaust gas, so the yield of the final purified material is very low compared with the original material, and A problem with a contaminated vacuum pump.
第二,在高真空狀態下注入載氣的過程中,未提純的原始試樣發生飛散,導致原始試樣受污染,在提純後,為了回收所提純的有機材料而使真空狀態通氣的過程中,有可能在完成提純的各試樣之間產生分散現象,因而具有導致所要得到的有機材料的最終純度下降的問題。 Second, during the process of injecting the carrier gas under high vacuum, the unpurified original sample scatters, causing the original sample to be contaminated. After purification, the vacuum state is ventilated in order to recover the purified organic material. Among them, there is a possibility that a dispersion phenomenon occurs between the respective samples which are purified, and thus there is a problem that the final purity of the organic material to be obtained is lowered.
第三,為了在完成提純製程後回收提純物質,需在使整體系統的真空氣氛恢復成常壓後停止整個系統,因此難以實現自動化。 Third, in order to recover the purified material after the purification process is completed, it is necessary to stop the entire system after restoring the vacuum atmosphere of the entire system to normal pressure, so that it is difficult to achieve automation.
第四,由於上述原因,需反復進行提純製程,因而所消耗的能量大,這最終將成為有機材料的成本上升的原因。 Fourth, for the above reasons, the purification process needs to be repeated, and the energy consumed is large, which will eventually become the cause of the increase in the cost of the organic material.
因此,本發明研發了將在真空狀態下也穩定的離子液體用作液體篩檢程式,從而可以簡單地進行提純和生產出有機材料的利用離子液體的有機材料提純技術,並確認了在通過上述有機材料提純技術提純的有機材料的表面形成有保護層。 Therefore, the present invention has developed an ionic liquid which is also stable under a vacuum state as a liquid screening program, so that an organic material purification technique using an ionic liquid for purifying and producing an organic material can be simply performed, and it is confirmed that The surface of the organic material purified by the organic material purification technology is formed with a protective layer.
專利文獻 Patent literature
韓國特許登錄第10-0550942號 Korean franchise registration No. 10-0550942
韓國特許登錄第10-0674680號 Korean franchise registration number 10-0674680
韓國特許登錄第10-1296430號 Korean franchise registration No. 10-1296430
韓國特許登錄第10-1343487號 Korean franchise registration No. 10-1343487
韓國公開特許第10-2013-0096370號 Korean Public License No. 10-2013-0096370
鑒於以上的問題,本發明提供為了實現有機材料的高純度化,利用離子液體對有機材料進行提純,或者在提純後的有機材料的表面塗敷離子液體,來在有機材料的表面形成保護層。 In view of the above problems, the present invention provides a protective layer formed on the surface of an organic material by purifying an organic material with an ionic liquid or by applying an ionic liquid to the surface of the purified organic material in order to achieve high purity of the organic material.
本發明揭露的有機材料於提純後的有機材料的表面被離子液體(Ionic liquids)保護。 The organic material disclosed in the present invention is protected by an ionic liquid (Ionic liquids) on the surface of the purified organic material.
本發明另揭露的有機材料於提純後的有機材料 的表面被源於離子液體的成分保護。 The organic material of the invention disclosed in the purified organic material The surface is protected by components derived from ionic liquids.
本發明又另揭露的有機材料於提純後的有機材料的表面被構成離子液體的離子保護。 The organic material disclosed in the present invention is protected by ions constituting the ionic liquid on the surface of the purified organic material.
在一實施例中,通過將含有雜質的有機發光二極體(OLED)用有機材料溶解於上述離子液體並實施再結晶來生成上述有機材料。 In one embodiment, the organic material is produced by dissolving an organic light-emitting diode (OLED) containing an impurity in an ionic liquid with an organic material and performing recrystallization.
在另一實施例中,透過使含有雜質的上述有機發光二極體用有機材料溶解、汽化或昇華來溶解於上述離子液體。 In another embodiment, the ionic liquid is dissolved by dissolving, vaporizing or sublimating the organic light-emitting diode containing impurities with an organic material.
在又一實施例中,使含有雜質的上述有機發光二極體用有機材料的固相、液相或氣相的有機材料溶解於離子液體。 In still another embodiment, the organic light-emitting diode containing impurities is dissolved in an ionic liquid using an organic material of a solid phase, a liquid phase, or a gas phase of an organic material.
在又一實施例中,上述有機材料的表面被以化學方式結合的單一分子層的陰離子(anion)保護。 In yet another embodiment, the surface of the above organic material is protected by an anion of a chemically bonded single molecular layer.
在又一實施例中,透過昇華提純方法來對含有雜質的有機發光二極體用有機材料進行提純,從而生成提純後的上述有機材料。 In still another embodiment, the organic light-emitting diode containing the impurity is purified by an sublimation purification method to form the purified organic material.
根據本發明所揭露的有機材料,為了實現有機材料的高純度化,利用離子液體對有機材料進行提純,或者在提純後的有機材料的表面塗敷離子液體,來在有機材料的表面形成保護層,從而具有在大氣環境下也可便於使提純的有機材料穩定的優點。即,本發明可防止提純後的有機材料受 水分的影響,因此具有非常便於在大氣環境下對有機材料進行操作的優點。此外,本發明的有機材料可通過熱處理或使能量粒子相碰撞的方法來完全去除源於保護有機材料的表面的離子液體的成分,因而具有不會對元件製程產生任何不利影響的優點。 According to the organic material disclosed in the present invention, in order to achieve high purity of the organic material, the organic material is purified by an ionic liquid, or an ionic liquid is applied on the surface of the purified organic material to form a protective layer on the surface of the organic material. Thus, there is an advantage that it is also convenient to stabilize the purified organic material in an atmospheric environment. That is, the present invention can prevent the organic material after purification from being subjected to The effect of moisture, therefore, has the advantage of being very convenient for handling organic materials in the atmosphere. Further, the organic material of the present invention can completely remove the components of the ionic liquid derived from the surface protecting the organic material by heat treatment or collision of the energy particles, and thus has an advantage that it does not adversely affect the component process.
以上之關於本發明內容之說明及以下之實施方式之說明係用以示範與解釋本發明之原理,並且提供本發明之專利申請範圍更進一步之解釋。 The above description of the present invention and the following description of the embodiments of the present invention are intended to illustrate and explain the principles of the invention.
100、200、300、400、500‧‧‧有機材料提純裝置 100, 200, 300, 400, 500‧‧‧ organic material purification device
600、700‧‧‧提純裝置 600, 700‧‧·purification device
110‧‧‧裝載船 110‧‧‧Loading ship
111‧‧‧有機材料原料 111‧‧‧Organic materials
112‧‧‧第一加熱器 112‧‧‧First heater
113‧‧‧昇華氣體 113‧‧‧ Sublimation gas
114‧‧‧混合氣體 114‧‧‧ mixed gas
120‧‧‧處理腔室 120‧‧‧Processing chamber
130‧‧‧連接導管 130‧‧‧Connecting catheter
131‧‧‧第二加熱器 131‧‧‧second heater
140‧‧‧儲存槽 140‧‧‧ storage tank
141‧‧‧離子液體 141‧‧‧ ionic liquid
142‧‧‧第三加熱器 142‧‧‧ third heater
143‧‧‧提純材料 143‧‧‧ Purified materials
150‧‧‧真空泵 150‧‧‧vacuum pump
151、152、154‧‧‧閥 151, 152, 154‧ ‧ valves
153‧‧‧排出泵 153‧‧‧Draining pump
160‧‧‧非活性氣體供給源 160‧‧‧Inactive gas supply source
210‧‧‧外殼 210‧‧‧Shell
211‧‧‧上部外殼 211‧‧‧ upper shell
212‧‧‧下部外殼 212‧‧‧lower casing
213‧‧‧主真空泵 213‧‧‧Main vacuum pump
214‧‧‧輔助真空泵 214‧‧‧Auxiliary vacuum pump
220‧‧‧昇華機構 220‧‧‧Sublimation institutions
221‧‧‧昇華腔室 221‧‧‧Sublimation chamber
230、230A、230B‧‧‧捕集機構 230, 230A, 230B‧‧‧ capture agencies
231‧‧‧軸 231‧‧‧Axis
232、232A、232B‧‧‧葉片 232, 232A, 232B‧‧‧ blades
233‧‧‧驅動馬達 233‧‧‧Drive motor
234‧‧‧泵 234‧‧‧ pump
235‧‧‧供給孔 235‧‧‧Supply hole
237‧‧‧回收容器 237‧‧‧Recycling container
238‧‧‧迴圈泵 238‧‧‧Circle pump
239‧‧‧噴射管 239‧‧‧Steam tube
239a‧‧‧噴射孔 239a‧‧‧spray hole
240‧‧‧再結晶化機構 240‧‧‧Recrystallization Mechanism
241‧‧‧儲存槽 241‧‧‧ storage tank
250‧‧‧回收機構 250‧‧‧Recycling agency
251‧‧‧回收桶 251‧‧‧Recycling bin
260‧‧‧更換機構 260‧‧‧Replacement agency
310‧‧‧外殼 310‧‧‧ Shell
311‧‧‧真空泵 311‧‧‧Vacuum pump
315‧‧‧加熱器 315‧‧‧heater
320‧‧‧昇華機構 320‧‧‧Sublimation institutions
321‧‧‧裝載船 321‧‧‧Loading ship
330‧‧‧捕集機構 330‧‧‧ Capture agencies
331‧‧‧軸 331‧‧‧Axis
332‧‧‧葉片 332‧‧‧ leaves
333‧‧‧驅動馬達 333‧‧‧Drive motor
340‧‧‧再結晶化機構 340‧‧‧Recrystallization Mechanism
341‧‧‧儲存槽 341‧‧‧ storage tank
350‧‧‧噴射機構 350‧‧‧Injection mechanism
352‧‧‧連通孔 352‧‧‧Connected holes
354‧‧‧驅動泵 354‧‧‧ drive pump
355‧‧‧回收容器 355‧‧‧Recycling container
356‧‧‧迴圈泵 356‧‧‧Circle pump
360‧‧‧回收機構 360‧‧‧Recycling agency
361‧‧‧回收桶 361‧‧‧Recycling bin
370‧‧‧更換機構 370‧‧‧Replacement agency
430‧‧‧捕集機構 430‧‧ ‧ capture agency
431‧‧‧噴射配管 431‧‧‧jet piping
510‧‧‧外殼 510‧‧‧ Shell
530‧‧‧捕集機構 530‧‧‧ Capture agencies
531‧‧‧旋轉輥 531‧‧‧Rotating roller
532‧‧‧儲存槽 532‧‧‧ storage tank
540‧‧‧再結晶化機構 540‧‧‧Recrystallization Mechanism
541‧‧‧刮片 541‧‧‧Scrape
542‧‧‧收集槽 542‧‧‧ collecting trough
550‧‧‧回收機構 550‧‧‧Recycling agency
610‧‧‧熔解部 610‧‧‧Mechanization Department
620‧‧‧混合部 620‧‧‧Mixed Department
630‧‧‧迴圈部 630‧‧‧Return
640‧‧‧離子液體供給部 640‧‧‧Ionic Liquid Supply Department
710‧‧‧熔解部 710‧‧‧Mechanization Department
720‧‧‧汽化部 720‧‧‧Degradation Department
730‧‧‧捕集部 730‧‧‧ Capture Department
740‧‧‧迴圈部 740‧‧‧Return
S1‧‧‧固相的有機材料 S1‧‧‧ Solid phase organic materials
S2‧‧‧固相的有機材料 S2‧‧‧ Solid phase organic materials
L1‧‧‧液相的有機材料 L1‧‧‧ liquid organic materials
L2‧‧‧離子液體 L2‧‧‧ ionic liquid
L3‧‧‧混合液 L3‧‧‧ mixture
S2+L3‧‧‧混合物 S2+L3‧‧‧ mixture
V1‧‧‧汽化氣體 V1‧‧‧ vaporized gas
第1圖為根據本發明第一實施例的利用離子液體的有機材料提純裝置的結構關係的示意圖。 Fig. 1 is a schematic view showing the structural relationship of an organic material purifying apparatus using an ionic liquid according to a first embodiment of the present invention.
第2圖為根據本發明第二實施例的利用離子液體的垂直型有機材料提純裝置的結構關係的分解立體圖。 Fig. 2 is an exploded perspective view showing the structural relationship of a vertical type organic material purifying apparatus using an ionic liquid according to a second embodiment of the present invention.
第3圖為根據本發明第二實施例的利用離子液體的垂直型有機材料提純裝置的結構關係的結合立體圖。 Fig. 3 is a perspective view showing the structure of a vertical type organic material purifying apparatus using an ionic liquid according to a second embodiment of the present invention.
第4圖為對第2圖所示的有機材料提純裝置的一部分進行截取的結合立體圖。 Fig. 4 is a perspective view showing a combination of a part of the organic material purifying apparatus shown in Fig. 2 .
第5圖為對具有第2圖所示的捕集機構的變形例的有機材料提純裝置的一部分進行截取的結合立體圖。 Fig. 5 is a perspective view showing a part of an organic material purifying apparatus having a modification of the collecting mechanism shown in Fig. 2, taken along a line.
第6圖為對具有第2圖所示的捕集機構的另一變形例的有機材料提純裝置的一部分進行截取的結合立體圖。 Fig. 6 is a perspective view showing a combination of a part of the organic material purifying apparatus having another modification of the collecting mechanism shown in Fig. 2 .
第7圖為根據本發明第三實施例的利用離子液體的水準型有機材料提純裝置的結構關係的示意圖。 Fig. 7 is a view showing the structural relationship of a level-type organic material purifying apparatus using an ionic liquid according to a third embodiment of the present invention.
第8圖為根據本發明第四實施例的利用離子液體的噴射型有機材料提純裝置的結構關係的示意圖。 Fig. 8 is a view showing the structural relationship of a spray type organic material purifying apparatus using an ionic liquid according to a fourth embodiment of the present invention.
第9圖為根據本發明第五實施例的利用離子液體的輥型有機材料提純裝置的結構關係的示意圖。 Fig. 9 is a view showing the structural relationship of a roll-type organic material purifying apparatus using an ionic liquid according to a fifth embodiment of the present invention.
第10圖為根據本發明第六實施例的利用離子液體的液相有機材料的提純裝置的簡要框圖。 Fig. 10 is a schematic block diagram of a purifying apparatus for a liquid phase organic material using an ionic liquid according to a sixth embodiment of the present invention.
第11圖為根據本發明第七實施例的利用離子液體的氣相有機材料的提純裝置的簡要框圖。 Figure 11 is a schematic block diagram of a purification apparatus for a vapor phase organic material using an ionic liquid according to a seventh embodiment of the present invention.
第12a圖為用於製造水準型有機材料提純裝置的俯視圖。 Figure 12a is a top plan view of a leveling apparatus for producing a leveling organic material.
第12b圖為用於製造水準型有機材料提純裝置的主視圖。 Figure 12b is a front view of a purification apparatus for manufacturing a leveling organic material.
第12c圖為用於製造水準型有機材料提純裝置的側視圖。 Figure 12c is a side view of a purification apparatus for manufacturing a leveling organic material.
第13圖為根據第12a圖、第12b圖與第12c圖所示的設計圖來製造的水準型有機材料提純裝置的實物照片。 Figure 13 is a photograph of a material of a leveling organic material purifying apparatus manufactured according to the design drawings shown in Figures 12a, 12b and 12c.
第14a圖和第14b圖為對通過第13圖所示的水準型有機材料提純裝置進行提純之前的空穴傳輸層(HTL)材料基於在大氣環境中暴露的時間的Raman PL特性變化進行測定的曲線圖。 Figs. 14a and 14b are graphs showing changes in Raman PL characteristics of a hole transport layer (HTL) material before being purified by the leveling organic material purifying apparatus shown in Fig. 13 based on the time of exposure in an atmospheric environment. Graph.
第14c圖和第14d圖為對通過第13圖所示的水準型有機材料提純裝置進行提純之後的空穴傳輸層(HTL)材料基於在大氣環境中暴露的時間的Raman PL特性變化進行測定的曲 線圖。 Fig. 14c and Fig. 14d are graphs showing changes in the Raman PL characteristics of the hole transport layer (HTL) material after purification by the level-type organic material purifying apparatus shown in Fig. 13 based on the exposure time in the atmospheric environment. song line graph.
第15a圖及第15b圖為對通過第13圖所示的水準型有機材料提純裝置進行提純之前的空穴傳輸層材料基於在大氣環境中暴露的時間的PL特性變化進行測定的曲線圖。 Fig. 15a and Fig. 15b are graphs for measuring changes in PL characteristics of the hole transport layer material before purification by the level-type organic material purifying apparatus shown in Fig. 13 based on the time of exposure in an atmospheric environment.
第15c圖及第15d圖為對通過第13圖所示的水準型有機材料提純裝置進行提純之後的空穴傳輸層材料基於在大氣環境中暴露的時間的PL特性變化進行測定的曲線圖。 Fig. 15c and Fig. 15d are graphs for measuring changes in PL characteristics of the hole transport layer material after purification by the level-type organic material purifying apparatus shown in Fig. 13 based on the time of exposure in an atmospheric environment.
第16a為對通過第13圖所示的水準型有機材料提純裝置進行提純之前的空穴傳輸層材料基於在大氣環境中暴露的時間的表面形狀的變化進行拍攝的掃描電子顯微鏡(SEM,×1k)照片。 The 16th is a scanning electron microscope (SEM, ×1k) of the change in the surface shape of the hole transport layer material before the purification by the level-type organic material purifying apparatus shown in Fig. 13 based on the exposure time in the atmospheric environment. )photo.
第16b為對通過第13圖所示的水準型有機材料提純裝置進行提純之後的空穴傳輸層材料基於在大氣環境中暴露0小時的表面形狀的變化進行拍攝的掃描電子顯微鏡(SEM,×1k)照片。 16b is a scanning electron microscope (SEM, ×1k) of the hole transport layer material after the purification by the level-type organic material purifying apparatus shown in Fig. 13 based on the change in surface shape exposed to the atmosphere for 0 hours. )photo.
第16c為對通過第13圖所示的水準型有機材料提純裝置進行提純之後的空穴傳輸層材料基於在大氣環境中暴露24小時的表面形狀的變化進行拍攝的掃描電子顯微鏡(SEM,×1k)照片。 The 16th is a scanning electron microscope (SEM, ×1k) of the hole transport layer material after the purification by the level-type organic material purifying apparatus shown in Fig. 13 based on the change in the surface shape exposed to the atmosphere for 24 hours. )photo.
第16d為對通過第13圖所示的水準型有機材料提純裝置進行提純之後的空穴傳輸層材料基於在大氣環境中暴露48小時的表面形狀的變化進行拍攝的掃描電子顯微鏡(SEM,×1k) 照片。 The 16th is a scanning electron microscope (SEM, ×1k) of the hole transport layer material after the purification by the level-type organic material purifying apparatus shown in Fig. 13 based on the change in the surface shape exposed to the atmosphere for 48 hours. ) photo.
第17圖為表示通過圖13所示的水準型有機材料提純裝置提純的有機材料的特徵的X射線光電子能譜(XPS)的曲線圖。 Fig. 17 is a graph showing the X-ray photoelectron spectroscopy (XPS) of the characteristics of the organic material purified by the level-type organic material purifying apparatus shown in Fig. 13.
第18圖為在120℃的溫度下對提純後的有機材料進行1分鐘的熱處理後以X射線光電子能譜來對表面結構進行分析的曲線圖。 Fig. 18 is a graph showing the surface structure analysis by X-ray photoelectron spectroscopy after heat treatment of the purified organic material for 1 minute at a temperature of 120 °C.
離子液體(ionic liquid)為通過陽離子和陰離子的離子結合來形成的類似鹽的物質,在100℃以下的溫度下,以液體狀態存在,即使在高溫下,也穩定地以液體方式存在,上述離子液體的蒸氣壓幾乎為0,因而被稱為“綠色溶劑(Green solvent)”,作為環保溶劑備受矚目。並且,離子液體可溶解多種無機物、有機物、高分子物質,並可易於改變疏水性、溶解度、粘度、密度等物理化學特性,因而還被稱作“設計溶劑(Designer Solvent)”,理論上,可進行1018種以上的合成,因而作為溶劑,具有無限的可能性。即,離子液體具有不僅呈現出現有的有機溶劑所未有的多種特性,還可選擇並合成符合使用人員的意圖的溶劑的巨大的優點(離子液體的最新研究動向1-Overview,韓國仁荷大學超精密生物分離技術研究所,李尚賢、河成浩)。 An ionic liquid is a salt-like substance formed by ionic bonding of a cation and an anion, exists in a liquid state at a temperature of 100 ° C or lower, and stably exists in a liquid state even at a high temperature, the above-mentioned ion The vapor pressure of the liquid is almost zero, so it is called "Green solvent" and has attracted attention as an environmentally friendly solvent. Moreover, the ionic liquid can dissolve a variety of inorganic substances, organic substances, high molecular substances, and can easily change physical and chemical properties such as hydrophobicity, solubility, viscosity, density, etc., and is also called "Designer Solvent", in theory, Since 1018 or more types of synthesis are carried out, there is an infinite possibility as a solvent. That is, the ionic liquid has a large number of characteristics not only in the presence of an organic solvent which is not present, but also a solvent which can be selected and synthesized in accordance with the intention of the user (the latest research trend of the ionic liquid 1-Overview, Inha University, Korea) Institute of Ultra-precision Bioseparation Technology, Li Shangxian, He Chenghao).
另一方面,離子液體通過陽離子和陰離子的結構 變化來易於改變非揮發性、非可燃性、熱穩定性、高離子傳導率、電化學穩定性、高沸點等物理化學特性,因而作為多功能性的“設計溶劑”而備受矚目。這種離子液體可提高酶的活性和穩定性,還可易於實現分離過程,在環境/經濟方面也優選,因此,今後離子液體可在多個領域廣泛使用。(Thi Phuong Thuy Pham,Chul-Woong Cho,Yeoung-Sang Yun,"Environmental fate and toxicity of ionic liquids:A review",Water Research,44,2010,pp.352~372) On the other hand, the structure of ionic liquids through cations and anions The change is easy to change non-volatile, non-flammable, thermal stability, high ionic conductivity, electrochemical stability, high boiling point and other physical and chemical properties, and thus has attracted attention as a "design solvent" for versatility. Such an ionic liquid can improve the activity and stability of the enzyme, can also easily realize the separation process, and is also environmentally/economically preferable, and therefore, ionic liquids can be widely used in various fields in the future. (Thi Phuong Thuy Pham, Chul-Woong Cho, Yeoung-Sang Yun, "Environmental fate and toxicity of ionic liquids: A review", Water Research, 44, 2010, pp. 352-372)
本實施例的離子液體可利用由化學式1表示的1-丁基-3-甲基咪唑雙三氟甲磺醯亞胺(1-Butyl-3-methylimidazolium bis(trifluoromethyl sulfonyl)imide,BMIM TFSI),或由化學式2表示的1-辛基-3-甲基咪唑雙三氟甲磺醯亞胺(1-Octyl-3-methylimidazolium bis(trifluoromethyl sulfonyl)imide,OMIM TFSI)。或者還可以使用1-乙基-3-甲基咪唑雙三氟甲磺醯亞胺(1-Ethyl-3-methylimidazolium bis(trifluoromethyl sulfonyl)imide,EMIM TFSI)。 The ionic liquid of the present embodiment can utilize 1-Butyl-3-methylimidazolium bis (trifluoromethyl sulfonyl) imide (BMIM TFSI) represented by Chemical Formula 1, Or 1-octyl-3-methylimidazolium bis(trifluoromethyl sulfonyl)imide (OMIM TFSI) represented by Chemical Formula 2. Alternatively, 1-Ethyl-3-methylimidazolium bis (trifluoromethyl sulfonyl) imide (EMIM TFSI) can also be used.
如上所述的離子液體(1-丁基-3-甲基咪唑雙三氟甲磺醯亞胺、1-辛基-3-甲基咪唑雙三氟甲磺醯亞胺、1-乙基-3-甲基咪唑雙三氟甲磺醯亞胺)作為非揮發性有機溶劑,在有機(organic)物質和雜質以溶解-再結晶化的方式在離子液體中反復實施的過程中,由於更快達到過飽和度的有機材料優先再結晶化的機制,可用於多種有機材料的提純及再結晶化。 Ionic liquid as described above (1-butyl-3-methylimidazolium bistrifluoromethanesulfonimide, 1-octyl-3-methylimidazolium bistrifluoromethanesulfonimide, 1-ethyl- 3-methylimidazolium bistrifluoromethanesulfonimide) as a non-volatile organic solvent, in the process of repeated implementation in an ionic liquid in the form of dissolution and recrystallization of organic substances and impurities, due to faster The mechanism of preferential recrystallization of organic materials that achieve supersaturation can be used for purification and recrystallization of various organic materials.
另一方面,1-丁基-3-甲基咪唑雙三氟甲磺醯亞胺、1-辛基-3-甲基咪唑雙三氟甲磺醯亞胺、1-乙基-3-甲基咪唑雙三氟甲磺醯亞胺具有低熔點(low melting point)、低蒸氣壓(low vapor pressure)、不易燃性(nonflammable)、有機分子離子的結構(consist of organic molecular ions)、陰離子-陽離子之間的組合比率的可調節性(controllable properties by combinations of anions and cations)等特性。 On the other hand, 1-butyl-3-methylimidazolium bistrifluoromethanesulfonimide, 1-octyl-3-methylimidazolium bistrifluoromethanesulfonimide, 1-ethyl-3-methyl Imidazole bistrifluoromethanesulfonimide has a low melting point, a low vapor pressure, a nonflammable, a composition of organic molecular ions, an anion Characteristics such as controllable properties by combinations of anions and cations.
本實施例的離子液體用於對有機材料進行提純及再結晶化,在100℃~120℃的溫度範圍、10-7Torr的壓力下也穩定地呈液體狀,從而還可在真空製程中用作溶劑。 The ionic liquid of the present embodiment is used for purifying and recrystallizing an organic material, and is stably liquid in a temperature range of 100 ° C to 120 ° C and a pressure of 10 -7 Torr, thereby being used in a vacuum process. As a solvent.
另一方面,構成有機發光二極體的核心材料可大致分為電荷傳輸用材料(空穴注入層、空穴傳輸層、電子注 入層、電子傳輸層)和發光用材料(螢光材料、磷光材料及各自的摻雜物)。這種有機發光二極體的總厚度為100~200nm左右,形成為超薄膜。另一方面,在電荷傳輸用材料中,作為空穴傳輸物質,可舉出N,N-二苯基-N,N-(1-萘基)-1,1-聯苯-4,4-二胺(NPB,N,N'-bis(naphthalen-1-yl)-N,N'-bis(phenyl)-benzidine)、N,N'-二苯基-N,N'-二(3-甲基苯基)-1,1'-聯苯-4,4'-二胺(TPD,N,N'-Bis-(2-methylphenyl)-N,N'-bis(phenyl)-benzidin)、N,N'-二苯基-N,N'-(1-萘基)-1,1'-聯苯-4,4'-二胺(NPD,N,N'-Di(naphthalen-1-yl)-N,N'-dibenzylbenzidine)、銅酞菁(CuPc,Copper Phthalocyanine)、4,4',4"-三(N-3-甲基苯基-N-苯基氨基)三苯胺(MTDATA,4,4',4"-tris(2-methylphenylamino)triphenylamine)等,而作為電子傳輸物質,可舉出三(8-羥基喹啉)鋁(Alq3,Tri-(8-hydroxy-chinolinato)-aluminium)、4,4-二(2,2-1-苯乙基)-二苯基(DTVBi,4,4-Bis(2,2-diphenyethen-1-yl)-diphenyl)等化合物,並且,作為發光用物質可舉出三(8-羥基喹啉)鋁、香豆素(coumarine)衍生物、喹吖啶酮(quinacridone)衍生物、紅熒烯(rubrene)等。 On the other hand, the core material constituting the organic light-emitting diode can be roughly classified into a material for charge transport (hole injection layer, hole transport layer, electron injection). In-layer, electron transport layer) and luminescent materials (fluorescent materials, phosphorescent materials, and respective dopants). The organic light-emitting diode has a total thickness of about 100 to 200 nm and is formed into an ultra-thin film. On the other hand, among the materials for charge transport, examples of the hole transporting material include N,N-diphenyl-N,N-(1-naphthyl)-1,1-biphenyl-4,4- Diamine (NPB, N, N'-bis (naphthalen-1-yl)-N, N'-bis(phenyl)-benzidine), N, N'-diphenyl-N, N'-di(3- Methylphenyl)-1,1'-biphenyl-4,4'-diamine (TPD, N, N'-Bis-(2-methylphenyl)-N, N'-bis(phenyl)-benzidin), N,N'-diphenyl-N,N'-(1-naphthyl)-1,1'-biphenyl-4,4'-diamine (NPD, N, N'-Di (naphthalen-1- Yl)-N,N'-dibenzylbenzidine), copper phthalocyanine (CuPc, Copper Phthalocyanine), 4,4',4"-tris(N-3-methylphenyl-N-phenylamino)triphenylamine (MTDATA) 4,4',4"-tris(2-methylphenylamino)triphenylamine), etc., and as the electron transporting substance, tris(8-hydroxyquinoline)aluminum (Alq3, Tri-(8-hydroxy-chinolinato)- Alkyl), 4,4-di(2,2-1-phenethyl)-diphenyl (DTVBi, 4,4-Bis(2,2-diphenyethen-1-yl)-diphenyl), and the like, Examples of the light-emitting substance include tris(8-hydroxyquinoline)aluminum, a coumarine derivative, a quinacridone derivative, and rubrene.
因此,本實施例的有機材料的原料可使用N,N-二苯基-N,N-(1-萘基)-1,1-聯苯-4,4-二胺材料。在這裡,N,N-二苯基-N,N-(1-萘基)-1,1-聯苯-4,4-二胺的昇華點為180℃以 上。因此,只要將收容有機材料原料的裝載船加熱至200℃以上的溫度,就能使有機材料原料昇華。 Therefore, the N,N-diphenyl-N,N-(1-naphthyl)-1,1-biphenyl-4,4-diamine material can be used as the raw material of the organic material of the present embodiment. Here, the sublimation point of N,N-diphenyl-N,N-(1-naphthyl)-1,1-biphenyl-4,4-diamine is 180 ° C. on. Therefore, the organic material raw material can be sublimated by heating the loading vessel containing the organic material raw material to a temperature of 200 ° C or higher.
另一方面,用於製造有機發光二極體元件的蒸鍍物質(有機材料原料)除如上所述的物質之外,還有很多種。即,本發明可將構成有機發光二極體的電荷傳輸用材料或發光用材料的多種有機材料用作原料。 On the other hand, there are many types of vapor deposition materials (organic material materials) for producing an organic light-emitting diode element in addition to the materials described above. That is, in the present invention, various organic materials constituting the charge transport material or the light-emitting material constituting the organic light-emitting diode can be used as a raw material.
藉此,本發明可將如上所述的多種離子液體作為液體篩檢程式來對如上所述的多種有機發光二極體用有機材料原料進行提純。 Thereby, the present invention can purify a plurality of organic material raw materials for organic light-emitting diodes as described above by using various ionic liquids as described above as a liquid screening program.
但是,有機材料除了如上所述的可用作有機發光二極體元件的發光體或傳輸體的低分子有機發光材料之外,還有有機薄膜電晶體(TFT)材料、有機太陽能電池材料、有機半導體材料等。因此,本發明可應用於如上所述的多種領域所適用的有機材料的提純,以下將以有機發光二極體用有機材料作為舉例來進行說明。 However, in addition to the low molecular organic light-emitting material which can be used as an illuminant or a transport body of an organic light-emitting diode element as described above, there are organic thin film transistor (TFT) materials, organic solar cell materials, and organic materials. Semiconductor materials, etc. Therefore, the present invention can be applied to the purification of an organic material which is applicable to various fields as described above, and an organic material for an organic light-emitting diode will be described below as an example.
以下,利用離子液體來對含有雜質的有機發光二極體用有機材料進行提純,參照附圖圖示來對利用如使用載氣(例如,非活性氣體)或不使用載氣的多種提純裝置來對有機材料進行提純的概念進行詳細說明。 Hereinafter, an organic material for an organic light-emitting diode containing impurities is purified by an ionic liquid, and various purification apparatuses such as a carrier gas (for example, an inert gas) or a carrier gas are used as illustrated with reference to the drawings. The concept of purification of organic materials is described in detail.
一、載體型的有機材料提純裝置 1. Carrier type organic material purification device
<第一實施例> <First Embodiment>
第1圖為根據本發明第一實施例的利用離子液 體的有機材料提純裝置的結構關係的示意圖。如第1圖所示,本實施例的有機材料提純裝置100包括:昇華部,用於使含有雜質的有機發光二極體用有機材料昇華;以及捕集部,以與昇華部相連通的方式配置,並使有機材料的昇華氣體與離子液體相接觸來捕集昇華氣體。在這裡,捕集部起到在由離子液體捕集並被溶解的昇華氣體中,優先使作為組成結構的主要成分的提純對象有機材料過飽和,從而生成再結晶化的高純度有機材料的作用。 Figure 1 is a view showing the use of an ionic liquid according to a first embodiment of the present invention. Schematic diagram of the structural relationship of the bulk organic material purification device. As shown in FIG. 1, the organic material purifying apparatus 100 of the present embodiment includes a sublimation portion for sublimating an organic light-emitting diode containing an organic material, and a trap portion communicating with the sublimation portion. The configuration and the sublimation gas of the organic material are contacted with the ionic liquid to capture the sublimation gas. Here, the trapping unit functions to supersaturate the organic material for purification which is a main component of the constituent structure in the sublimation gas which is collected and dissolved by the ionic liquid, thereby generating a recrystallized high-purity organic material.
上述捕集部包括:捕集機構,使昇華後的有機材料的昇華氣體強制向離子液體流動,並與離子液體相接觸,來捕集昇華氣體;以及再結晶化機構,在借助捕集機構來捕集於離子液體並被溶解的昇華氣體中,優先使作為組成結構的主要成分的提純對象有機材料過飽和,從而生成再結晶化的高純度有機材料。而且,昇華部包括昇華機構,上述昇華機構用於加熱含有雜質的有機發光二極體用有機材料原料來使其昇華。 The trapping unit includes a trapping mechanism for forcibly flowing a sublimation gas of the sublimated organic material toward the ionic liquid, and contacting the ionic liquid to trap the sublimation gas; and a recrystallization mechanism, by means of the trapping mechanism In the sublimation gas trapped in the ionic liquid and dissolved, the organic material for purification which is a main component of the constituent structure is preferentially supersaturated to form a recrystallized high-purity organic material. Further, the sublimation unit includes a sublimation mechanism for heating the organic material for organic light-emitting diodes containing impurities to sublimate them.
另一方面,優選地,本實施例的有機材料提純裝置100還包括昇華機構、捕集機構及用於控制再結晶化機構的啟動的控制機構。在這裡,昇華氣體具有使將要進行提純的有機材料從固體狀態昇華為氣體狀態,或從固體狀態昇華為凝膠狀態,並以氣體狀態蒸發的總括概念。 On the other hand, preferably, the organic material purifying apparatus 100 of the present embodiment further includes a sublimation mechanism, a trapping mechanism, and a control mechanism for controlling activation of the recrystallization mechanism. Here, the sublimation gas has an overall concept of sublimating the organic material to be purified from a solid state to a gaseous state, or sublimating from a solid state to a gel state, and evaporating in a gaseous state.
昇華機構包括:裝載船110,用於收容有機材料 原料111;處理腔室120,設置有裝載船110,並具有規定的內部體積;真空泵150,用於使處理腔室120的內部成為真空狀態;以及第一加熱器112,用於對裝載船110進行加熱。而且,捕集機構包括非活性氣體供給源160,上述非活性氣體供給源160與處理腔室120的一側相連接,用於供給非活性氣體。 The sublimation mechanism includes: a loading vessel 110 for accommodating organic materials a raw material 111; a processing chamber 120 provided with a loading vessel 110 and having a prescribed internal volume; a vacuum pump 150 for making the interior of the processing chamber 120 into a vacuum state; and a first heater 112 for loading the vessel 110 Heat up. Further, the trap mechanism includes an inert gas supply source 160 that is connected to one side of the processing chamber 120 for supplying an inert gas.
此外,再結晶化機構包括:儲存槽140,用於收容離子液體141;連接導管130,上述連接導管130的一側與處理腔室120的內部相連通,上述連接導管130的另一側浸漬於儲存槽140內的離子液體141;上述真空泵150,用於將儲存槽140的內部形成為真空狀態;以及排出泵153,向儲存槽140的外部排出收集於儲存槽140的離子液體141之上的氣體。 Further, the recrystallization mechanism includes a storage tank 140 for accommodating the ionic liquid 141, a connection duct 130, one side of the connection duct 130 communicates with the inside of the processing chamber 120, and the other side of the connection duct 130 is immersed in The ionic liquid 141 in the storage tank 140; the vacuum pump 150 for forming the inside of the storage tank 140 into a vacuum state; and the discharge pump 153 discharging the ionic liquid 141 collected on the storage tank 140 to the outside of the storage tank 140 gas.
另一方面,處理腔室120和儲存槽140在上側相互連接,在它們的連接部位設置有真空泵150。而且,在真空泵150的連接線上分別設置有用於選擇性地與處理腔室120及儲存槽140相連通的閥151、152。 On the other hand, the processing chamber 120 and the storage tank 140 are connected to each other on the upper side, and a vacuum pump 150 is provided at their connection portions. Further, valves 151, 152 for selectively communicating with the processing chamber 120 and the storage tank 140 are provided on the connecting line of the vacuum pump 150, respectively.
裝載船110設置於處理腔室120的底面側,上述裝載船110以在下部側具有第一加熱器112的方式構成。並且,裝載船110呈可在上述裝載船110的內部裝載作為提純對象的有機材料原料111的形態。 The loading ship 110 is disposed on the bottom surface side of the processing chamber 120, and the loading ship 110 is configured to have the first heater 112 on the lower side. Further, the loading ship 110 has a form in which the organic material raw material 111 to be purified can be loaded inside the loading ship 110.
另一方面,連接導管130的一側與處理腔室120 的上部相連接,連接導管130的另一側經由儲存槽140的上部來延伸,並以浸漬於離子液體141的內部的形態配置。在這種連接導管130的周圍還可設置有用於加熱連接導管130的第二加熱器131。在這裡,第二加熱器131起到在將要後述的混合氣體經由連接導管130向離子液體141內流入的過程中,以使混合昇華氣體113維持昇華點的方式加熱連接導管130的周圍的作用。 On the other hand, the side connecting the conduit 130 and the processing chamber 120 The upper portion of the connection duct 130 is connected to the other side via the upper portion of the storage tank 140, and is disposed so as to be immersed in the inside of the ionic liquid 141. A second heater 131 for heating the connection duct 130 may also be disposed around the connection duct 130. Here, the second heater 131 serves to heat the periphery of the connection duct 130 such that the mixed sublimation gas 113 maintains the sublimation point in the process of flowing the mixed gas to be described later into the ionic liquid 141 via the connection duct 130.
而且,在儲存槽140的下部還可設置有第三加熱器142。在這裡,第三加熱器142起到加熱離子液體141來調節混合昇華氣體113溶解於離子液體141的溶解度的作用。並且,在儲存槽140的上部側還可設置有排出泵153。此時,優選地,在排出泵153的設置線還設置有閥154。 Moreover, a third heater 142 may be disposed at a lower portion of the storage tank 140. Here, the third heater 142 functions to heat the ionic liquid 141 to adjust the solubility of the mixed sublimation gas 113 in the ionic liquid 141. Further, a discharge pump 153 may be further disposed on the upper side of the storage tank 140. At this time, preferably, a valve 154 is further provided at the set line of the discharge pump 153.
以下,對利用以如上所述的方式構成的本實施例的有機材料提純裝置來對有機材料進行提純的方法進行說明。 Hereinafter, a method of purifying an organic material by using the organic material purifying apparatus of the present embodiment configured as described above will be described.
首先,在處理腔室120的內部設置裝有有機材料原料111的裝載船110,在向儲存槽140注入適當量的離子液體141後,利用真空泵150使處理腔室120和儲存槽140形成真空狀態。之後,利用第一加熱器112加熱裝載船110至有機材料的昇華點。從而成為有機材料和部分雜質混合的有機材料的混合昇華氣體113。 First, a loading vessel 110 containing an organic material raw material 111 is disposed inside the processing chamber 120. After an appropriate amount of the ionic liquid 141 is injected into the storage tank 140, the processing chamber 120 and the storage tank 140 are vacuumed by the vacuum pump 150. . Thereafter, the loading vessel 110 is heated by the first heater 112 to the sublimation point of the organic material. Thereby, it becomes a mixed sublimation gas 113 of an organic material in which an organic material and a part of impurities are mixed.
在此狀態下,從非活性氣體供給源160向處理腔 室120的內部供給非活性氣體。此時,非活性氣體可在防止真空度過於下降的範圍內使用不與構成有機材料提純裝置100的材料發生反應的氮氣或氬氣等。這種非活性氣體起到用於使混合昇華氣體113向儲存槽140內的離子液體141流動的作用,因此,與混合昇華氣體113混合來成為混合氣體。 In this state, from the inert gas supply source 160 to the processing chamber The interior of the chamber 120 is supplied with an inert gas. At this time, the inert gas can use nitrogen gas or argon gas which does not react with the material constituting the organic material purification device 100 in a range in which the degree of vacuum is prevented from being excessively lowered. This inert gas acts to flow the mixed sublimation gas 113 to the ionic liquid 141 in the storage tank 140, and therefore is mixed with the mixed sublimation gas 113 to become a mixed gas.
隨著處理腔室120的內部的壓力上升,以這種方式形成的混合氣體114經由連接導管130向離子液體141混入,從而形成氣泡。另一方面,在混合氣體114經由連接導管130向離子液體141混入的過程中,設置於連接導管130的周圍的第二加熱器131加熱連接導管130的周圍,隨之,混合昇華氣體113可以以維持昇華點的狀態混入離子液體141中。 As the pressure inside the processing chamber 120 rises, the mixed gas 114 formed in this manner is mixed into the ionic liquid 141 via the connection duct 130, thereby forming bubbles. On the other hand, in the process in which the mixed gas 114 is mixed into the ionic liquid 141 via the connection duct 130, the second heater 131 disposed around the connection duct 130 heats the circumference of the connection duct 130, and accordingly, the mixed sublimation gas 113 can be The state in which the sublimation point is maintained is mixed into the ionic liquid 141.
另一方面,混入離子液體141的混合氣體形成氣泡,並使氣泡中的混合昇華氣體113溶解於離子液體141,非活性氣體以不溶解於離子液體141的狀態向離子液體141外上升,從而收集於儲存槽140的上部。像這樣,收集於儲存槽140的上部的非活性氣體借助排出泵153向儲存槽140外排出並被回收。另一方面,向儲存槽140外排出並被回收的非活性氣體通過氣體返回機構來向非活性氣體供給源160返回,因此,還可迴圈利用。在這裡,非活性氣體返回機構利用普通的泵等來構成。 On the other hand, the mixed gas mixed in the ionic liquid 141 forms a bubble, and the mixed sublimation gas 113 in the bubble is dissolved in the ionic liquid 141, and the inert gas rises outside the ionic liquid 141 without being dissolved in the ionic liquid 141, thereby collecting In the upper part of the storage tank 140. In this manner, the inert gas collected in the upper portion of the storage tank 140 is discharged to the outside of the storage tank 140 by the discharge pump 153 and is recovered. On the other hand, the inert gas discharged to the outside of the storage tank 140 and recovered is returned to the inert gas supply source 160 through the gas return mechanism, and therefore, it can be recycled. Here, the inert gas returning mechanism is constituted by a general pump or the like.
當混合昇華氣體113溶解於離子液體141時,相 對於雜質,提純物件中的有機材料的含量絕對高於雜質,因而有機材料優先達到過飽和狀態,並首先開始再結晶化,從而析出為高純度的提純材料143。此時,可利用設置於儲存槽140的下部的第三加熱器142來調節混合昇華氣體113溶解於離子液體141的溶解度。由此,可調節離子液體141對昇華氣體113的溶解度,來控制離子液體141內的有機材料的過飽和度及有機材料的再結晶化速度等。由此,可在再結晶化的過程中將雜質的混入最小化,而這樣析出於離子液體141內的高純度的提純材料143只要從儲存槽140適當回收即可。例如,只要在儲存槽140的一側形成開閉口來通過該開閉口回收提純材料143即可。 When the mixed sublimation gas 113 is dissolved in the ionic liquid 141, the phase For the impurities, the content of the organic material in the purified article is absolutely higher than that of the impurities, so that the organic material preferentially reaches the supersaturation state, and first begins to recrystallize, thereby precipitating the purified material 143 of high purity. At this time, the solubility of the mixed sublimation gas 113 dissolved in the ionic liquid 141 can be adjusted by the third heater 142 provided at the lower portion of the storage tank 140. Thereby, the solubility of the ionic liquid 141 to the sublimation gas 113 can be adjusted to control the degree of supersaturation of the organic material in the ionic liquid 141, the recrystallization rate of the organic material, and the like. Thereby, the mixing of impurities can be minimized in the process of recrystallization, and the high-purity purification material 143 thus precipitated in the ionic liquid 141 can be appropriately recovered from the storage tank 140. For example, an opening and closing port may be formed on one side of the storage tank 140 to recover the purification material 143 through the opening and closing port.
如上所述,若回收析出於離子液體141內的高純度的提純材料143,則混合氣體內所包含的溶解至達到過飽和度之前的有機材料和少量的雜質將部分殘留於離子液體141內。並且,隨著提純製程的進行,離子液體141內的雜質的含量增加,且在規定時間點,雜質成分也達到過飽和度,因而將產生雜質混入再結晶化的有機材料內。優選地,在該時間點上,將用於提純製程的離子液體更換為高純度的離子液體。 As described above, when the high-purity purification material 143 precipitated in the ionic liquid 141 is recovered, the organic material and a small amount of impurities contained in the mixed gas dissolved until the supersaturation is reached partially remain in the ionic liquid 141. Further, as the purification process progresses, the content of impurities in the ionic liquid 141 increases, and the impurity component also reaches the supersaturation at a predetermined time point, so that impurities are mixed into the recrystallized organic material. Preferably, at this point in time, the ionic liquid used in the purification process is replaced with a high purity ionic liquid.
二、無載體型的有機材料提純裝置 Second, the carrier-free organic material purification device
2-1、有機材料的昇華氣體提純技術 2-1. Sublimation gas purification technology for organic materials
<第二實施例> <Second embodiment>
第2圖為根據本發明第二實施例的利用離子液體的垂直型有機材料提純裝置的結構關係的分解立體圖。第3圖為根據本發明第二實施例的利用離子液體的垂直型有機材料提純裝置的結構關係的結合立體圖。第4圖為第2圖所示的有機材料提純裝置的一部分進行截取的結合立體圖。 Fig. 2 is an exploded perspective view showing the structural relationship of a vertical type organic material purifying apparatus using an ionic liquid according to a second embodiment of the present invention. Fig. 3 is a perspective view showing the structure of a vertical type organic material purifying apparatus using an ionic liquid according to a second embodiment of the present invention. Fig. 4 is a perspective view showing a part of the organic material purifying apparatus shown in Fig. 2 taken along a line.
如第2圖所示,本實施例的有機材料提純裝置200包括:昇華部,用於使含有雜質的有機發光二極體用有機材料昇華;以及捕集部,以與昇華部相連通的方式配置,並使有機材料的昇華氣體與流動的離子液體相接觸來捕集昇華氣體。在這裡,捕集部起到在由離子液體捕集並被溶解的昇華氣體中,優先使作為組成結構的主要成分的提純對象有機材料過飽和,從而生成再結晶化的高純度有機材料的作用。 As shown in FIG. 2, the organic material purifying apparatus 200 of the present embodiment includes: a sublimation portion for sublimating an organic light-emitting diode containing impurities with an organic material; and a trap portion communicating with the sublimation portion The sublimation gas of the organic material is placed in contact with the flowing ionic liquid to capture the sublimation gas. Here, the trapping unit functions to supersaturate the organic material for purification which is a main component of the constituent structure in the sublimation gas which is collected and dissolved by the ionic liquid, thereby generating a recrystallized high-purity organic material.
如第2圖至第4圖所示,上述捕集部包括:真空氣氛的外殼210,具有規定的內部體積;捕集機構230,使昇華後的有機材料的昇華氣體與離子液體相接觸,來捕集昇華氣體;以及再結晶化機構240,在因捕集機構230而捕集於離子液體並被溶解的昇華氣體中,優先使作為組成結構的主要成分的提純對象有機材料過飽和,從而生成再結晶化的高純度有機材料。 As shown in FIGS. 2 to 4, the trap portion includes a vacuum atmosphere outer casing 210 having a predetermined internal volume, and a trap mechanism 230 for contacting the sublimated gas of the sublimed organic material with the ionic liquid. The sublimation gas is collected, and the recrystallization unit 240 supersaturate the organic material to be purified, which is a main component of the constituent structure, in the sublimation gas that is trapped in the ionic liquid and is dissolved by the trap mechanism 230, thereby generating Crystallized high purity organic material.
此外,昇華部包括多個昇華機構220,上述多個昇華機構220分別與外殼210的下部側相連通,來加熱含有雜質的有機發光二極體用有機材料原料並使其昇華。 Further, the sublimation unit includes a plurality of sublimation mechanisms 220, and the plurality of sublimation mechanisms 220 communicate with the lower side of the outer casing 210 to heat and sublimate the organic material for the organic light-emitting diode containing impurities.
另一方面,優選地,本實施例的有機材料提純裝置200還包括控制機構(未圖示),上述控制機構(未圖示)用於控制昇華機構220、捕集機構230及再結晶化機構240的啟動。 On the other hand, preferably, the organic material purifying apparatus 200 of the present embodiment further includes a control mechanism (not shown) for controlling the sublimation mechanism 220, the trapping mechanism 230, and the recrystallization mechanism. Start of 240.
外殼210具有與外部相封閉的規定的內部體積,上述外殼210包括:上部外殼211,用於構成上部側;下部外殼212,與上部外殼211的下部相結合;主真空泵213,將外殼210的內部形成為真空狀態;以及輔助真空泵214,用於細微調節外殼210的內部的真空度。 The outer casing 210 has a predetermined inner volume closed to the outside, and the outer casing 210 includes an upper outer casing 211 for forming an upper side, a lower outer casing 212 coupled with a lower portion of the upper outer casing 211, and a main vacuum pump 213 for inner portion of the outer casing 210. Formed in a vacuum state; and an auxiliary vacuum pump 214 for finely adjusting the degree of vacuum inside the outer casing 210.
昇華機構220包括:昇華腔室221,與下部外殼212相結合;裝載船(未圖示),配置于昇華腔室221的內部,用於收容有機材料原料;以及加熱器(未圖示),用於加熱裝載船。 The sublimation mechanism 220 includes a sublimation chamber 221 coupled to the lower casing 212, a loading vessel (not shown) disposed inside the sublimation chamber 221 for accommodating the raw material of the organic material, and a heater (not shown), Used to heat the loading vessel.
令外,捕集機構230包括:中空形態的軸231,沿著外殼210的中心軸設置;葉片232,沿著軸231的周圍面以螺旋形態設置;驅動馬達233,與軸231的上端相結合,用於供給動力;泵234,用於向軸231的內部供給離子液體;以及多個供給孔(未圖示),以沿著葉片232的上部面及下部面供給離子液體的方式形成於軸231。 Further, the trap mechanism 230 includes a hollow shaft 231 disposed along a central axis of the outer casing 210, a vane 232 disposed in a spiral shape along a peripheral surface of the shaft 231, and a drive motor 233 coupled to the upper end of the shaft 231. a pump 234 for supplying an ionic liquid to the inside of the shaft 231, and a plurality of supply holes (not shown) for forming an ionic liquid along the upper surface and the lower surface of the blade 232. 231.
上述葉片232沿著軸231的周圍面來以螺旋形態設置,隨著外殼210具有圓錐形形態,與之相對應地,上述葉片232以從上部越朝向下部,寬度越大的形態構成。即, 葉片232以橫穿昇華氣體飛散的路徑的方式配置於外殼210內,以外殼210內的垂直軸為中心,以相同角度配置。 The vane 232 is provided in a spiral shape along the peripheral surface of the shaft 231, and the vane 232 has a conical shape, and the vane 232 is configured to have a larger width from the upper portion toward the lower portion. which is, The vane 232 is disposed in the outer casing 210 so as to traverse the path in which the sublimation gas scatters, and is disposed at the same angle centering on the vertical axis in the outer casing 210.
另一方面,葉片232還可以包括以留有上下間隔的方式固定於軸231的多個渦輪葉片,來代替如上所述的連續的螺旋型葉片。即,隨著使葉片232以非連續性的類型構成,可使離子液體經由葉片之間的空間向下部方向流動。 On the other hand, the vane 232 may further include a plurality of turbine blades fixed to the shaft 231 in a manner of leaving the upper and lower intervals instead of the continuous spiral vanes as described above. That is, as the blade 232 is configured in a discontinuous type, the ionic liquid can flow in the downward direction via the space between the blades.
本實施例的有機材料提純裝置200還可包括:回收機構250,用於回收得到提純、析出並沉澱於儲存槽241的下部的有機材料;以及更換機構260,用於更換收容有有機材料原料的新的裝載船和有機材料原料得到昇華的空裝載船。 The organic material purifying apparatus 200 of the present embodiment may further include: a recovery mechanism 250 for recovering the organic material which is purified, precipitated and precipitated in the lower portion of the storage tank 241; and a replacement mechanism 260 for replacing the raw material containing the organic material. New loading vessels and raw materials for organic materials are sublimated empty loading vessels.
以下,對利用以如上所述的方式構成的本實施例的垂直型有機材料提純裝置來對有機材料進行提純的方法進行說明。 Hereinafter, a method of purifying an organic material using the vertical organic material purifying apparatus of the present embodiment configured as described above will be described.
首先,在昇華腔室221的內部設置裝有有機材料原料的裝載船,並驅動泵234及驅動馬達233來對整個葉片232的上部面及下部面和外殼210的內側面塗敷離子液體。之後,利用主真空泵213來對外殼210及昇華腔室221的內部實施真空化。 First, a loading ship equipped with an organic material raw material is disposed inside the sublimation chamber 221, and a pump 234 and a drive motor 233 are driven to apply ionic liquid to the upper surface and the lower surface of the entire blade 232 and the inner surface of the outer casing 210. Thereafter, the inside of the outer casing 210 and the sublimation chamber 221 is vacuumed by the main vacuum pump 213.
然後,利用加熱器來加熱裝載船至有機材料原料的昇華點為止,之後間隔1~5分鐘,並加熱至昇華點以上。由此,成為混合有有機材料和部分雜質的有機材料的昇華氣 體。另一方面,從形成有機材料的昇華氣體的時間點開始,使離子液體沿著葉片232的上部面及下部面流動。即,借助泵234以規定的壓力向軸231的內部供給離子液體,而借助驅動馬達233的驅動力,軸231旋轉,並使離子液體經由多個供給孔來沿著葉片232的上部面及下部面流動。並且,通過設置於外殼210的外側面的加熱器,在外殼210的內部形成便於使有機材料再結晶化的溫度氣氛。 Then, the heater is used to heat the loading vessel to the sublimation point of the organic material, and then after 1 to 5 minutes, and heated to above the sublimation point. Thereby, it becomes a sublimation gas of an organic material mixed with an organic material and a part of impurities. body. On the other hand, the ionic liquid flows along the upper surface and the lower surface of the blade 232 from the time point when the sublimation gas of the organic material is formed. That is, the ionic liquid is supplied to the inside of the shaft 231 by the pump 234 at a predetermined pressure, and the shaft 231 is rotated by the driving force of the drive motor 233, and the ionic liquid is passed along the upper surface and the lower portion of the blade 232 via the plurality of supply holes. Surface flow. Further, a temperature atmosphere that facilitates recrystallization of the organic material is formed inside the outer casing 210 by the heater provided on the outer surface of the outer casing 210.
像這樣,離子液體沿著葉片232的上部面及下部面流動,當調節板被開放時,有機材料的昇華氣體向外殼210的內部流動,並經由葉片232自然地向外殼210的上部側飛散,從而使離子液體和昇華氣體與葉片232的上部面及下部面等相接觸。借助這種接觸,昇華氣體在被捕集於離子液體後,逐漸被溶解、再結晶化,並聚集於外殼210的下部的儲存槽241。即,當昇華氣體溶解于離子液體時,由於相對於雜質的提純物件的有機材料的含量絕對高於雜質,因而有機材料優先達到過飽和狀態,並先開始再結晶化,從而析出為高純度的有機材料。 In this manner, the ionic liquid flows along the upper surface and the lower surface of the vane 232, and when the regulating plate is opened, the sublimation gas of the organic material flows into the inside of the outer casing 210, and naturally scatters toward the upper side of the outer casing 210 via the vane 232. Thereby, the ionic liquid and the sublimation gas are brought into contact with the upper surface and the lower surface of the blade 232. With this contact, the sublimation gas is gradually dissolved, recrystallized, and collected in the storage tank 241 at the lower portion of the outer casing 210 after being trapped in the ionic liquid. That is, when the sublimation gas is dissolved in the ionic liquid, since the content of the organic material of the purified article relative to the impurity is absolutely higher than the impurity, the organic material preferentially reaches a supersaturation state, and starts to recrystallize, thereby precipitating into a high-purity organic substance. material.
另一方面,可利用設置於上部外殼211及下部外殼212的外側面的加熱器來調節混合昇華氣體溶解於離子液體的溶解度。由此,調節離子液體與昇華氣體之間的溶解度,從而可控制離子液體內的有機材料的過飽和度及有機材料的再結晶化速度等。由此,可在再結晶化的過程中將雜質的混 入最小化,而以這種方式析出於離子液體內的高純度的有機材料只要從外殼210儲存槽241適當地回收即可。 On the other hand, the heaters provided on the outer surfaces of the upper casing 211 and the lower casing 212 can be used to adjust the solubility of the mixed sublimation gas in the ionic liquid. Thereby, the solubility between the ionic liquid and the sublimation gas is adjusted, whereby the degree of supersaturation of the organic material in the ionic liquid, the recrystallization rate of the organic material, and the like can be controlled. Thereby, the impurities can be mixed during the recrystallization process. The miniaturization is minimized, and the high-purity organic material which is precipitated in the ionic liquid in this manner is appropriately recovered from the storage tank 241 of the outer casing 210.
例如,若再結晶化的有機材料沉澱於離子液體的下部,則只要通過與儲存槽241相連接的回收機構250的回收桶251來回收提純的有機材料即可。但是,若再結晶化的有機材料不沉澱於離子液體的下部,而漂浮於離子液體的表面或混合於離子液體內,則只要在向儲存槽241的外部排出儲存槽241內的混合液和再結晶化的有機材料後,借助過濾或離心分析等方式使再結晶化的有機材料分離,並回收於回收容器237後,利用迴圈泵238使混合液向捕集機構230側重新迴圈即可。 For example, if the recrystallized organic material is precipitated in the lower portion of the ionic liquid, the purified organic material may be recovered by the recovery tank 251 of the recovery mechanism 250 connected to the storage tank 241. However, if the recrystallized organic material does not precipitate in the lower portion of the ionic liquid and floats on the surface of the ionic liquid or is mixed in the ionic liquid, the mixture in the storage tank 241 is discharged to the outside of the storage tank 241 and then After the crystallized organic material is separated, the recrystallized organic material is separated by filtration or centrifugal analysis, and recovered in the recovery container 237, and then the mixture liquid is recirculated to the collecting mechanism 230 side by the loop pump 238. .
第5圖為對具有第2圖所示的捕集機構的變形例的有機材料提純裝置的一部分進行截取的結合立體圖。如第5圖所示,變形例的捕集機構230A具有沿著軸231的周圍面設置的多個葉片232A,除此之外的結構要素以與捕集機構230相同的方式構成。在這裡,葉片232A向垂直方向排列,來從上部向下部側具有順時針方向的迴旋角。即,葉片232A的一側端部至另一側端部的相位差達到例如120度左右的迴旋角。因此,多個葉片232A以橫穿昇華氣體所飛散的路徑的方式配置於外殼210內,並以外殼210內的垂直軸為中心,以相同角度配置。 Fig. 5 is a perspective view showing a part of an organic material purifying apparatus having a modification of the collecting mechanism shown in Fig. 2, taken along a line. As shown in FIG. 5, the collecting mechanism 230A of the modification has a plurality of blades 232A provided along the peripheral surface of the shaft 231, and the other components are configured in the same manner as the collecting mechanism 230. Here, the vanes 232A are arranged in the vertical direction to have a clockwise turning angle from the upper portion to the lower side. That is, the phase difference from one end to the other end of the blade 232A reaches a swing angle of, for example, about 120 degrees. Therefore, the plurality of blades 232A are disposed in the casing 210 so as to traverse the path through which the sublimation gas is scattered, and are disposed at the same angle around the vertical axis in the casing 210.
第6圖為對具有第2圖所示的捕集機構的另一變 形例的有機材料提純裝置的一部分進行截取的結合立體圖。如第6圖所示,另一變形例的捕集機構230B包括:多個葉片232B,向軸231的長度方向沿著上述軸231的周圍面以具有等間距的方式設置;以及多個噴射管239,與多個供給孔235相連通,來向葉片232B的表面積上部外殼的內側面噴射朝向軸231的內部供給的離子液體,而除此之外的結構要素以與捕集機構230相同的方式構成。在這裡,葉片232B以向軸231的長度方向沿著上述軸231的周圍面以具有等間距的方式設置,並配置于昇華氣體飛散的路徑上來旋轉。即,多個葉片232B以橫穿昇華氣體飛散的路徑的方式配置於外殼210內,並以外殼210內的垂直軸為中心,以相同角度配置。 Figure 6 is another variation of the capture mechanism shown in Figure 2 A combined perspective view of a portion of the organic material purification device of the form is taken. As shown in Fig. 6, the collecting mechanism 230B of another modification includes a plurality of blades 232B which are disposed at equal intervals along the circumferential surface of the shaft 231 in the longitudinal direction of the shaft 231, and a plurality of injection tubes. 239, in communication with the plurality of supply holes 235, ejecting the ionic liquid supplied toward the inside of the shaft 231 toward the inner surface of the upper surface of the surface of the blade 232B, and the other components are configured in the same manner as the trap mechanism 230. . Here, the vane 232B is provided at equal intervals along the circumferential surface of the shaft 231 in the longitudinal direction of the shaft 231, and is disposed to rotate on the path in which the sublimation gas is scattered. That is, the plurality of blades 232B are disposed in the casing 210 so as to traverse the path in which the sublimation gas scatters, and are disposed at the same angle around the vertical axis in the casing 210.
而且,噴射管239以三角形形狀上下配置於葉片232B之間,來向葉片232B的表面及上部外殼211的內側面均勻地噴射離子液體。在這種噴射管239分別形成有用於噴射離子液體的多個噴射孔239a,此時,優選地,噴射孔239a朝向葉片232B的表面及上部外殼的內側面,並如擴散噴嘴,可按噴霧方式噴射離子液體。 Further, the injection pipe 239 is disposed vertically between the blades 232B in a triangular shape to uniformly spray the ionic liquid toward the surface of the blade 232B and the inner surface of the upper casing 211. In the spray pipe 239, a plurality of injection holes 239a for spraying the ionic liquid are respectively formed. At this time, preferably, the injection holes 239a face the surface of the blade 232B and the inner side surface of the upper casing, and as a diffusion nozzle, may be sprayed. Spray ionic liquid.
<第三實施例> <Third embodiment>
第7圖為根據本發明第三實施例的利用離子液體的水準型有機材料提純裝置的結構關係的示意圖。如第7圖所示,本實施例的有機材料提純裝置300除多個葉片配置成以外殼內的水準軸為中心,隔開相同角度來旋轉之外,以 與第二實施例的有機材料提純裝置200相同的概念構成。因此,在本實施例中,將省略對與第二實施例重複的部分的說明。 Fig. 7 is a view showing the structural relationship of a level-type organic material purifying apparatus using an ionic liquid according to a third embodiment of the present invention. As shown in FIG. 7, the organic material purifying apparatus 300 of the present embodiment is configured such that the plurality of blades are arranged to rotate around the same angle by the horizontal axis in the outer casing, The same conceptual configuration as the organic material purifying apparatus 200 of the second embodiment. Therefore, in the present embodiment, the description of the portions overlapping with the second embodiment will be omitted.
外殼310具有與外部封閉的規定的內部體積,上述外殼310包括真空泵311,上述真空泵311將外殼310的內部形成為真空狀態。昇華機構320包括:裝載船321,用於收容有機材料原料;以及加熱器(未圖示),用於加熱裝載船321。而且,捕集機構330包括:軸331,沿著外殼310的水準中心軸設置;多個葉片332,沿著軸331的周圍面設置;以及驅動馬達333,與軸331的一側端部相結合,來供給動力。 The outer casing 310 has a predetermined inner volume closed to the outside, and the outer casing 310 includes a vacuum pump 311 which forms the inside of the outer casing 310 into a vacuum state. The sublimation mechanism 320 includes a loading ship 321 for accommodating an organic material raw material, and a heater (not shown) for heating the loading ship 321 . Moreover, the trap mechanism 330 includes a shaft 331 disposed along a level central axis of the outer casing 310, a plurality of blades 332 disposed along a peripheral surface of the shaft 331, and a drive motor 333 coupled to one end of the shaft 331 To supply power.
另一方面,本實施例的有機材料提純裝置300還可包括:噴射機構350,用於向昇華氣體流動的側方路徑的下部側噴射離子液體;回收機構360,用於回收在形成於外殼310的再結晶化機構340的儲存槽341再結晶化並沉澱的有機材料;以及更換機構370,用於更換收容有有機材料原料的新的裝載船和有機材料原料得到昇華的空裝載船。在這裡,噴射機構350起到以橫穿昇華氣體飛散的路徑來落下的方式供給離子液體的離子液體供給機構的作用。 On the other hand, the organic material purifying apparatus 300 of the present embodiment may further include: an ejecting mechanism 350 for ejecting the ionic liquid to the lower side of the side path of the sublimation gas flow; and a recovery mechanism 360 for recycling in the outer casing 310 The storage tank 341 of the recrystallization mechanism 340 recrystallizes and precipitates the organic material; and the replacement mechanism 370 is used to replace the new loading vessel and the organic material raw material containing the raw material of the organic material to obtain a sublimated empty loading vessel. Here, the injection mechanism 350 functions as an ionic liquid supply mechanism that supplies the ionic liquid so as to fall across the path in which the sublimation gas scatters.
以下,對利用以如上所述的方式構成的本實施例的水準型有機材料提純裝置來對有機材料進行提純的方法進行說明。 Hereinafter, a method of purifying an organic material by using the level-type organic material purifying apparatus of the present embodiment configured as described above will be described.
首先,在外殼310的內部設置裝有有機材料原料 的裝載船321,驅動泵354、迴圈泵356及驅動馬達333來對整個葉片332的表面和外殼310的內側面塗敷離子液體。之後,利用真空泵311來對外殼310的內部實施真空化。 First, an organic material is placed inside the outer casing 310. The loading vessel 321, the drive pump 354, the loop pump 356, and the drive motor 333 apply ionic liquid to the surface of the entire vane 332 and the inner side of the outer casing 310. Thereafter, the inside of the outer casing 310 is vacuumed by the vacuum pump 311.
然後,利用加熱器來加熱裝載船321至有機材料原料的昇華點為止,之後間隔1~5分鐘,並加熱至昇華點以上。由此,成為混合有有機材料和部分雜質的有機材料的昇華氣體。另一方面,從形成有機材料的昇華氣體的時間點開始,啟動泵354及迴圈泵356,並通過連通孔352噴射昇華氣體,並且,啟動驅動馬達333來使葉片332旋轉,從而使昇華氣體向外殼310的另一側方向流動。並且,通過設置於外殼310的外側面的加熱器315,在外殼310的內部形成便於使有機材料再結晶化的溫度氣氛。 Then, the heater is used to heat the loading vessel 321 to the sublimation point of the organic material, and then after 1 to 5 minutes, and heated to above the sublimation point. Thereby, it becomes a sublimation gas of the organic material in which the organic material and partial impurities are mixed. On the other hand, from the time point of forming the sublimation gas of the organic material, the pump 354 and the loop pump 356 are activated, and the sublimation gas is injected through the communication hole 352, and the drive motor 333 is activated to rotate the blade 332, thereby causing the sublimation gas Flows toward the other side of the outer casing 310. Further, a temperature atmosphere that facilitates recrystallization of the organic material is formed inside the outer casing 310 by the heater 315 provided on the outer surface of the outer casing 310.
藉此,昇華氣體向外殼310的另一側方向流動,來使葉片332的表面與離子液體相接觸,並且,與通過連通孔352噴射的離子液體相接觸。借助這種接觸,昇華氣體在被捕集於離子液體後,逐漸被溶解、再結晶化,並聚集於外殼310的下部的儲存槽341。即,當昇華氣體溶解于離子液體時,由於相對於雜質的提純物件的有機材料的含量絕對高於雜質,因而有機材料優先達到過飽和狀態,並先開始再結晶化,從而析出為高純度的有機材料。 Thereby, the sublimation gas flows toward the other side of the outer casing 310 to bring the surface of the vane 332 into contact with the ionic liquid, and is in contact with the ionic liquid ejected through the communication hole 352. With this contact, the sublimation gas is gradually dissolved, recrystallized, and collected in the storage tank 341 at the lower portion of the outer casing 310 after being trapped in the ionic liquid. That is, when the sublimation gas is dissolved in the ionic liquid, since the content of the organic material of the purified article relative to the impurity is absolutely higher than the impurity, the organic material preferentially reaches a supersaturation state, and starts to recrystallize, thereby precipitating into a high-purity organic substance. material.
另一方面,可利用設置於外殼310的外側面的加熱器315來調節昇華氣體溶解於離子液體的溶解度。由此, 調節離子液體與昇華氣體之間的溶解度,從而可控制離子液體內的有機材料的過飽和度及有機材料的再結晶化速度等。由此,可在再結晶化的過程中將雜質的混入最小化,而以這種方式析出於離子液體內的高純度的有機材料只要從外殼310儲存槽341適當回收即可。 On the other hand, the heater 315 provided on the outer side surface of the outer casing 310 can be used to adjust the solubility of the sublimation gas dissolved in the ionic liquid. thus, The solubility between the ionic liquid and the sublimation gas is adjusted to control the supersaturation of the organic material in the ionic liquid, the recrystallization rate of the organic material, and the like. Thereby, the mixing of impurities can be minimized in the process of recrystallization, and the high-purity organic material which is precipitated in the ionic liquid in this manner can be appropriately recovered from the storage tank 341 of the outer casing 310.
例如,若再結晶化的有機材料沉澱於離子液體的下部,則只要通過與儲存槽341相連接的回收機構360的回收桶361來回收提純的有機材料即可。但是,若再結晶化的有機材料不沉澱於離子液體的下部,而漂浮於離子液體的表面或混合於離子液體內,則只要在向儲存槽341的外部排出儲存槽341內的混合液和再結晶化的有機材料後,借助過濾或離心分析等的方式使再結晶化的有機材料分離,並回收於回收容器355後,利用迴圈泵356使混合液向捕集機構330側重新迴圈即可。 For example, if the recrystallized organic material is precipitated in the lower portion of the ionic liquid, the purified organic material may be recovered by the recovery tank 361 of the recovery mechanism 360 connected to the storage tank 341. However, if the recrystallized organic material does not precipitate in the lower portion of the ionic liquid and floats on the surface of the ionic liquid or is mixed in the ionic liquid, the mixture in the storage tank 341 is discharged to the outside of the storage tank 341 and then After the crystallized organic material is separated, the recrystallized organic material is separated by filtration or centrifugal analysis, and collected in the recovery container 355, and then the liquid mixture is recirculated to the collecting mechanism 330 by the loop pump 356. can.
<第四實施例> <Fourth embodiment>
第8圖為根據本發明第四實施例的利用離子液體的噴射型有機材料提純裝置的結構關係的示意圖。如第8圖所示,在本實施例的有機材料提純裝置400中,捕集機構430由橫穿昇華氣體飛散的路徑來以簾狀或多種形態噴射離子液體的噴射機構構成。即,噴射機構起到以橫穿昇華氣體飛散的路徑來落下的方式供給離子液體的離子液體供給機構的作用。因此,本實施例的有機材料提純裝置400除了省略 捕集機構330,且變更一部分噴射單元350之外,以與第三實施例的有機材料提純裝置300相同的方式構成。因此,在本實施例中,省略對與第三實施例相同的結構要素的說明。 Fig. 8 is a view showing the structural relationship of a spray type organic material purifying apparatus using an ionic liquid according to a fourth embodiment of the present invention. As shown in Fig. 8, in the organic material purifying apparatus 400 of the present embodiment, the trapping mechanism 430 is constituted by an ejecting mechanism that ejects the ionic liquid in a curtain shape or a plurality of forms across a path in which the sublimation gas scatters. That is, the injection mechanism functions as an ionic liquid supply mechanism that supplies the ionic liquid so as to fall across the path in which the sublimation gas scatters. Therefore, the organic material purification device 400 of the present embodiment is omitted except The trap mechanism 330 is configured in the same manner as the organic material purifying apparatus 300 of the third embodiment except that a part of the ejecting unit 350 is changed. Therefore, in the present embodiment, the description of the same constituent elements as those of the third embodiment will be omitted.
本實施例的捕集機構430由分別具有用於噴射離子液體的多個噴嘴的多個噴射配管431構成。此時,多個噴射配管431向昇華氣體飛散的路徑方向以留有規定間隔的方式設置,使得通過各噴嘴以簾狀或多種形態從上部向下部噴射的離子液體與昇華氣體相接觸。在這裡,優選地,多個噴射配管431設置成以Z字方式配置有多個噴嘴,使得飛散的昇華氣體全部與離子液體相接觸,並逐漸被捕集。 The collecting mechanism 430 of the present embodiment is constituted by a plurality of injection pipes 431 each having a plurality of nozzles for ejecting an ionic liquid. At this time, the plurality of injection pipes 431 are disposed in a direction in which the sublimation gas scatters at a predetermined interval so that the ionic liquid ejected from the upper portion to the lower portion through the respective nozzles in a curtain shape or a plurality of forms is in contact with the sublimation gas. Here, preferably, the plurality of injection pipes 431 are disposed such that a plurality of nozzles are arranged in a zigzag manner such that the scattered sublimation gases are all in contact with the ionic liquid and are gradually collected.
<第五實施例> <Fifth Embodiment>
第9圖為根據本發明第五實施例的利用離子液體的輥型有機材料提純裝置的結構關係的示意圖。如第9圖所示,在本實施例的有機材料提純裝置500中,除了在捕集機構530設有以橫穿昇華氣體飛散的路徑的方式配置於外殼510內的一個以上的旋轉輥531,在再結晶化機構540設有配置於旋轉輥531的一側部來用於從旋轉輥531的表面除去昇華氣體溶解於離子液體而生成的混合液的刮片541之外,以與第三實施例的有機材料提純裝置300相同的概念構成。因此,在本實施例中,省略對與第三實施例重複的部分的說明。 Fig. 9 is a view showing the structural relationship of a roll-type organic material purifying apparatus using an ionic liquid according to a fifth embodiment of the present invention. As shown in FIG. 9, in the organic material purifying apparatus 500 of the present embodiment, in addition to the collecting mechanism 530, one or more rotating rolls 531 disposed in the outer casing 510 so as to traverse the path of the sublimation gas are disposed. The recrystallization mechanism 540 is provided with a blade 541 disposed on one side of the rotating roller 531 for removing the mixed liquid generated by dissolving the sublimated gas in the ionic liquid from the surface of the rotating roller 531, and the third embodiment The organic material purification device 300 of the example has the same concept. Therefore, in the present embodiment, the description of the portions overlapping with the third embodiment will be omitted.
本實施例的捕集機構530包括:一個以上的旋轉輥531,以橫穿昇華氣體飛散的路徑的方式配置於外殼510 內;以及儲存槽532,配置於旋轉輥531的下部,來向旋轉輥531的表面供給離子液體。在這裡,旋轉輥531以下部側浸漬於儲存在儲存槽532的離子液體的狀態旋轉。因此,離子液體塗敷於旋轉輥531的表面,昇華氣體與以這種方式塗敷的離子液體的表面相接觸來捕集並溶解。由此,在旋轉輥531的表面生成昇華氣體溶解於離子液體的混合液。另一方面,可在外殼510內以並列的方式配置多個旋轉輥531。 The trap mechanism 530 of the present embodiment includes one or more rotating rollers 531 disposed on the outer casing 510 so as to traverse the path of the sublimation gas scattering. The inside and the storage tank 532 are disposed at a lower portion of the rotating roller 531 to supply the ionic liquid to the surface of the rotating roller 531. Here, the lower side of the rotating roller 531 is immersed in the state in which the ionic liquid stored in the storage tank 532 is rotated. Therefore, the ionic liquid is applied to the surface of the rotating roller 531, and the sublimed gas is brought into contact with the surface of the ionic liquid coated in this manner to be trapped and dissolved. Thereby, a mixed liquid in which the sublimation gas is dissolved in the ionic liquid is generated on the surface of the rotating roller 531. On the other hand, a plurality of rotating rollers 531 may be arranged in parallel in the outer casing 510.
本實施例的再結晶化機構540包括:刮片541,配置於旋轉輥531的一側部來用於從旋轉輥531的表面除去上述混合液;以及收集槽542,收集借助刮片541來回收的混合液,使得有機材料過飽和,從而生成再結晶化的有機材料。另一方面,再結晶化的有機材料只要通過與收集槽542相連接的其他回收機構550來回收即可。 The recrystallization mechanism 540 of the present embodiment includes a doctor blade 541 disposed at one side of the rotating roller 531 for removing the mixed liquid from the surface of the rotating roller 531, and a collecting tank 542 which is collected and collected by the blade 541. The mixture makes the organic material supersaturated to form a recrystallized organic material. On the other hand, the recrystallized organic material may be recovered by another recovery mechanism 550 connected to the collection tank 542.
2-2、液相有機材料的提純技術 2-2. Purification technology of liquid organic materials
<第六實施例> <Sixth embodiment>
第10圖為根據本發明第六實施例的利用離子液體的液相有機材料的提純裝置的簡要框圖。如第10圖所示,本實施例的提純裝置600包括:熔解部,用於使含有雜質的固相的有機材料S1熔解,來生成液相的有機材料L1;混合部620,混合從熔解部610供給的液相的有機材料L1和離子液體L2(ionic liquids;ILs)來形成混合物S2+L3,並優先使作為組成結構的主要成分的提純對象有機材料過飽和,從 而生成再結晶化的固相有機材料;以及迴圈部630,從混合部620排出混合部620的混合物S2+L3來分離固相的有機材料S2後,使剩餘混合液L3向上述混合部620迴圈。上述混合部620的一側與供給離子液體L1的離子液體供給部640相連接。 Fig. 10 is a schematic block diagram of a purifying apparatus for a liquid phase organic material using an ionic liquid according to a sixth embodiment of the present invention. As shown in Fig. 10, the purification apparatus 600 of the present embodiment includes a melting section for melting the solid phase organic material S1 containing impurities to form a liquid phase organic material L1, and a mixing section 620 for mixing from the melting section. The organic material L1 and the ionic liquids (ILs) of the liquid phase supplied by 610 form a mixture S2+L3, and preferentially supersaturate the organic material for purification as a main component of the constituent structure, from The recrystallized solid phase organic material is generated, and the loop portion 630 is discharged from the mixing portion 620 to the mixture S2+L3 of the mixing portion 620 to separate the solid phase organic material S2, and then the remaining mixed liquid L3 is passed to the mixing portion 620. Loop. One side of the mixing unit 620 is connected to the ionic liquid supply unit 640 to which the ionic liquid L1 is supplied.
以下,對利用以如上所述的方式構成的本實施例的液相有機材料的提純裝置來對有機材料進行提純的方法進行說明。 Hereinafter, a method of purifying an organic material by using a purification apparatus of a liquid phase organic material of the present embodiment configured as described above will be described.
首先,在熔解部610熔解含有雜質的固相有機材料S1,來生成液相的有機材料L1。之後,向混合部620分別供給在熔解部610所生成的液相的有機材料L1和離子液體供給部640的離子液體L2,並在混合部620混合液相的有機材料L1和離子液體L2,來形成混合物S2+L3。另一方面,通過如上所述的混合過程,在混合部620優先使作為組成結構的主要成分的提純對象有機材料過飽和,從而再結晶化為固相有機材料S2。之後,從混合部620排出混合部620的混合物S2+L3來分離固相的有機材料S2後,利用迴圈部630來使剩餘混合液L3回到混合部620,並重新利用。 First, the solid phase organic material S1 containing impurities is melted in the melting unit 610 to form an organic material L1 in the liquid phase. Thereafter, the organic material L1 of the liquid phase generated in the melting unit 610 and the ionic liquid L2 of the ionic liquid supply unit 640 are supplied to the mixing unit 620, and the organic material L1 and the ionic liquid L2 of the liquid phase are mixed in the mixing unit 620. A mixture S2+L3 is formed. On the other hand, the mixing target 620 preferentially supersaturates the organic material for purification which is the main component of the composition structure by the mixing process as described above, thereby recrystallizing into the solid phase organic material S2. Thereafter, the mixture S2+L3 of the mixing unit 620 is discharged from the mixing unit 620 to separate the organic material S2 of the solid phase, and then the remaining mixture liquid L3 is returned to the mixing unit 620 by the loop portion 630, and reused.
2-3、有機材料的汽化氣體提純技術 2-3. Vaporization gas purification technology for organic materials
<第七實施例> <Seventh embodiment>
第11圖為根據本發明第七實施例的利用離子液體的氣相有機材料的提純裝置的簡要框圖。如第11圖所示, 本實施例的提純裝置700包括:熔解部710,用於使含有雜質的固相的有機材料S1熔解,來生成液相的有機材料L1;汽化部720,使從熔解部710供給的液相的有機材料L1蒸發,來生成有機材料的汽化氣體V1;捕集部730,使從汽化部720供給的有機材料的汽化氣體V1與流動的離子液體L2相接觸,使汽化氣體V1捕集為離子液體L2並得到溶解;以及迴圈部740,接收在捕集部730生成的混合物S2+L3來分離固相的有機材料S2後,使剩餘混合液L3向捕集部730迴圈。 Figure 11 is a schematic block diagram of a purification apparatus for a vapor phase organic material using an ionic liquid according to a seventh embodiment of the present invention. As shown in Figure 11, The purification apparatus 700 of the present embodiment includes a melting section 710 for melting an organic material S1 of a solid phase containing impurities to form an organic material L1 of a liquid phase, and a vaporization section 720 for supplying a liquid phase supplied from the melting section 710. The organic material L1 is evaporated to generate a vaporized gas V1 of the organic material; the trap portion 730 brings the vaporized gas V1 of the organic material supplied from the vaporization portion 720 into contact with the flowing ionic liquid L2, and traps the vaporized gas V1 as an ionic liquid. L2 is dissolved; and the loop portion 740 receives the mixture S2+L3 generated in the trap portion 730 to separate the solid phase organic material S2, and then loops the remaining mixed liquid L3 to the trap portion 730.
另一方面,捕集部730起到在捕集於離子液體L2並被溶解的汽化氣體V1中,優先使作為組成結構的主要成分的提純對象有機材料過飽和,從而生成再結晶化的固相的有機材料S2的作用。而且,捕集部730的一側與用於供給離子液體L1的離子液體供給部750相連接。 On the other hand, the trapping unit 730 supersaturate the organic material for purification which is a main component of the constituent structure in the vaporized gas V1 which is collected and dissolved in the ionic liquid L2, thereby generating a recrystallized solid phase. The role of organic material S2. Further, one side of the trap portion 730 is connected to the ionic liquid supply portion 750 for supplying the ionic liquid L1.
以下,對利用以如上所述的方式構成的本實施例的氣相有機材料的提出裝置來對有機材料進行提純的方法進行說明。 Hereinafter, a method of purifying an organic material by using a vapor phase organic material presenting apparatus of the present embodiment configured as described above will be described.
首先,在熔解部710使含有雜質的固相的有機材料S1熔解,來生成液相的有機材料L1,並使以這種方式生成的液相的有機材料L1在汽化部720進行汽化,從而生成有機材料的汽化氣體V1。之後,向捕集部730分別供給在汽化部740生成的有機材料的汽化氣體V1和離子液體供給部750的離子液體L2,使有機材料的汽化氣體V1捕集於離子液體 L2並被溶解,從而得到混合液L3和固相的有機材料S2。即,在捕集部730,優先使作為組成結構的組要成分的提純物件有機材料過飽和,從而再結晶化為固相的有機材料S2。之後,使捕集部730的混合物L3+S2迴圈,來分離固相的有機材料S2,並使剩餘混合液L3重新利用於有機材料的汽化氣體V1的捕集。 First, the solid material S1 containing the solid phase of the impurity is melted in the melting unit 710 to form the organic material L1 in the liquid phase, and the organic material L1 in the liquid phase generated in this manner is vaporized in the vaporization unit 720 to generate The vaporized gas V1 of the organic material. Thereafter, the vaporized gas V1 of the organic material generated in the vaporization unit 740 and the ionic liquid L2 of the ionic liquid supply unit 750 are supplied to the collecting unit 730, respectively, and the vaporized gas V1 of the organic material is trapped in the ionic liquid. L2 is dissolved to obtain a mixed liquid L3 and a solid phase organic material S2. In other words, in the collecting unit 730, the organic material S2 which is recrystallized into a solid phase is supersaturated by preferentially supersaturating the organic material which is a constituent component of the constituent structure. Thereafter, the mixture L3+S2 of the collecting unit 730 is looped to separate the organic material S2 of the solid phase, and the remaining mixed liquid L3 is reused for the collection of the vaporized gas V1 of the organic material.
以下,對本發明的有機材料的再結晶化機制進行說明。由於本發明的提純製程利用借助離子液體內的有機發光二極體用有機材料的濃度梯度來使氣相(昇華氣體、汽化氣體)或液相的有機發光二極體用有機材料再結晶化為固相的流程,而並不借助溫度梯度,因而可在更加接近熱力學平衡狀態的條件下,分離物件有機材料和雜質。此時,離子液體可維持在真空氣氛下加熱至規定溫度的狀態。即,由於離子液體的蒸氣壓非常低,因而在真空氣氛下加熱至規定溫度的狀態下,也不會揮發而維持液相,因此將離子液體用作有機材料提純的溶劑。 Hereinafter, the mechanism of recrystallization of the organic material of the present invention will be described. Since the purification process of the present invention utilizes the concentration gradient of the organic material for the organic light-emitting diode in the ionic liquid, the organic light-emitting diode of the gas phase (sublimation gas, vaporized gas) or liquid phase is recrystallized into an organic material. The solid phase process, without the aid of a temperature gradient, allows the separation of organic materials and impurities from objects closer to the thermodynamic equilibrium. At this time, the ionic liquid can be maintained in a state of being heated to a predetermined temperature in a vacuum atmosphere. In other words, since the vapor pressure of the ionic liquid is extremely low, the liquid phase is maintained without being volatilized while being heated to a predetermined temperature in a vacuum atmosphere. Therefore, the ionic liquid is used as a solvent for purifying the organic material.
若使氣相(昇華氣體、汽化氣體)或液相的含有雜質的有機發光二極體用有機材料捕集於加熱至規定溫度的離子液體並被溶解,則首先使在離子液體內形成主要結構的物件有機材料過飽和,此時,優先使物件有機材料再結晶化為固相,雜質將以溶解於離子液體內的狀態殘留。察看更加細微區域的反應如下,在離子液體內優先再結晶化的物件有 機材料的固相表面,不斷產生固體-液體之間的介面反應,此時,固相的有機材料為了通過維持固相內的均勻的組成來降低固相內的吉布斯能,自發性地反復形成向固相有機材料的外部(離子液體)排出雜質的反應。通過這種機制來實現再結晶化的固相的有機材料將維持簡單的單一相,最終,即使通過一次提純製程,也可得到高純度的有機材料。 When an organic light-emitting diode containing an impurity in a gas phase (sublimation gas, vaporized gas) or a liquid phase is trapped in an organic liquid heated to a predetermined temperature and dissolved, the main structure is first formed in the ionic liquid. The organic material of the object is supersaturated. At this time, the organic material of the object is preferentially recrystallized into a solid phase, and the impurities remain in a state of being dissolved in the ionic liquid. Look at the reactions in the more subtle areas as follows. The objects that are preferentially recrystallized in the ionic liquid are The solid phase surface of the machine material continuously produces a solid-liquid interface reaction. At this time, the solid phase organic material reduces the Gibbs energy in the solid phase by maintaining a uniform composition in the solid phase, spontaneously The reaction of discharging impurities to the outside (ionic liquid) of the solid phase organic material is repeatedly formed. The organic material which realizes the recrystallized solid phase by this mechanism will maintain a simple single phase, and finally, a high-purity organic material can be obtained even by a single purification process.
在上述的第一實施例中,以例示性的方式說明了利用離子液體對含有雜質的有機發光二極體用有機材料進行提純,並使有機材料的昇華氣體向載氣(例如,非活性氣體)流動來對有機材料進行提純的概念,在第二實施例至第五實施例中,以例示性的方式說明了不利用載氣而從有機材料的昇華氣體提純出有機材料的概念。而且,在第六實施例中,以例示性的方式說明了在將含有雜質的有機發光二極體用有機材料熔解為液相的狀態下進行提純的概念,在第七實施例中,以例示性的方式說明了對由含有雜質的有機發光二極體用有機材料在熔解成液相後蒸發而成的汽化氣體進行提純的概念。另一方面,在上述實施例中,說明了借助離子液體對液相或氣相的含有雜質的有機發光二極體用有機材料進行提純的概念,但根據有機材料的特性,也可借助離子液體對固相的有機材料進行提純。 In the first embodiment described above, the organic material for the organic light-emitting diode containing impurities is purified by an ionic liquid in an illustrative manner, and the sublimation gas of the organic material is directed to a carrier gas (for example, an inert gas). The concept of flowing to purify an organic material, in the second to fifth embodiments, illustrates the concept of purifying an organic material from a sublimation gas of an organic material without using a carrier gas in an illustrative manner. Further, in the sixth embodiment, the concept of purifying in the state in which the organic material for the organic light-emitting diode containing impurities is melted into a liquid phase is explained in an illustrative manner, and in the seventh embodiment, by way of illustration The qualitative method explains the concept of purifying a vaporized gas which is evaporated by an organic material containing an organic light-emitting diode containing impurities after being melted into a liquid phase. On the other hand, in the above embodiments, the concept of purifying an organic material for an organic light-emitting diode containing impurities in a liquid phase or a gas phase by means of an ionic liquid has been described, but depending on the characteristics of the organic material, an ionic liquid can also be used. The solid phase organic material is purified.
因此,可通過除如上所述的實施例以外的多種方法來利用離子液體對含有雜質的有機發光二極體用有機材料 進行提純。 Therefore, the organic material for the organic light-emitting diode containing impurities can be utilized by the ionic liquid by various methods other than the above-described embodiments. Purification.
但是,若用於有機發光二極體的有機發光材料暴露於大氣環境中,則其特性將急劇變差,尤其呈現出對水分脆弱的特性。即,若有機發光材料的烴基與水分子相結合,則有機材料的電特性,尤其導電性急劇下降,並呈現出電絕緣特性,導致元件特性急劇下降。因此,在有機發光材料的流通步驟中,應非常嚴格管理對水分的阻斷,在元件的製造製程中,阻斷水分也是非常重要的事項之一。 However, if the organic light-emitting material used for the organic light-emitting diode is exposed to the atmosphere, its characteristics will drastically deteriorate, and in particular, it exhibits a property of being weak to moisture. That is, when the hydrocarbon group of the organic light-emitting material is combined with water molecules, the electrical properties, particularly conductivity, of the organic material are drastically lowered, and electrical insulating properties are exhibited, resulting in a sharp drop in device characteristics. Therefore, in the flow of the organic light-emitting material, the blocking of moisture should be strictly regulated, and blocking moisture in the manufacturing process of the component is also one of the most important matters.
另一方面,本發明確認了即使將離子液體用作液體篩檢程式來對有機發光二極體用有機材料進行提純後,將提純的有機材料長時間暴露於大氣環境中,提純的有機材料的特性也未變差。這被判斷為是由離子液體的特性引起的。 On the other hand, the present invention has confirmed that even if an ionic liquid is used as a liquid screening program to purify an organic material for an organic light-emitting diode, the purified organic material is exposed to the atmosphere for a long time, and the purified organic material is used. The characteristics have not deteriorated. This was judged to be caused by the characteristics of the ionic liquid.
例如,確認到在對有機發光材料進行提純方面,若利用由咪唑鹽基(imidazolium)的陽離子(cation)和烷基磺酸鹽基(alkylsulfonates)的陰離子(anion)構成的離子液體,則在對提純的有機發光材料進行清洗後,在有機發光材料的表面以單一分子層的厚度存在化學結合形態的作為離子液體的陰離子的烷基磺酸鹽基。這種離子液體的陰離子形成具有疏水性特性的表面,從而具有防止水向有機發光材料的表面滲透的效果。 For example, it has been confirmed that in the purification of the organic light-emitting material, if an ionic liquid composed of an cation of an imidazolium and an anion of an alkylsulfonate is used, After the purified organic light-emitting material is washed, an alkylsulfonate group as an anion of the ionic liquid in a chemically bonded form exists in the thickness of a single molecular layer on the surface of the organic light-emitting material. The anion of such an ionic liquid forms a surface having hydrophobic properties, thereby having an effect of preventing water from penetrating into the surface of the organic light-emitting material.
因此,通過以單一分子層的方式塗敷具有這種疏水性特性的陰離子的技術,可阻斷有機發光材料受水分的影 響,由此,可非常便於在大氣環境中對有機發光材料進行操作,從而在有機發光二極體元件的製造製程中也可從源頭上防止水分滲透。 Therefore, by applying a technique having an anion having such a hydrophobic property in a single molecular layer, the moisture of the organic light-emitting material can be blocked. Therefore, it is very convenient to operate the organic light-emitting material in an atmospheric environment, so that moisture penetration can be prevented from the source in the manufacturing process of the organic light-emitting diode element.
如上所述,由於可通過二次處理技術(熱處理,或使高能粒子(energetic particle)碰撞的方法)來去除借助化學結構來塗敷于利用離子液體來提純的有機發光二極體用有機材料的表面的單一分子層的陰離子,因而可防止在元件的製造製程中混入雜質。 As described above, since the organic structure for the organic light-emitting diode for purification by the ionic liquid can be removed by a secondary treatment technique (heat treatment, or a method of causing collision of energetic particles) The anion of the single molecular layer of the surface prevents the inclusion of impurities in the manufacturing process of the component.
在這裡,能量粒子可使用離子束(ion beam)、等離子體(plasma)或電子束(electron beam)等,作為進行加熱的加熱機構,可使用普通的熱源、鐳射波(laser wave)或脈衝(紫外線(UV)、可見光(Visible)、紅外線(IR))等。另一方面,作為等離子設備,可使用氬等離子(Ar plasma)、氮等離子(N2 plasma),但並不局限於此。 Here, the energy particles may use an ion beam, a plasma, an electron beam or the like as a heating means for heating, and an ordinary heat source, a laser wave or a pulse may be used ( Ultraviolet (UV), visible light (Visible), infrared (IR), etc. On the other hand, as the plasma apparatus, Ar plasma or nitrogen plasma (N2 plasma) can be used, but it is not limited thereto.
以下,對包括利用如上所述的本發明的離子液體的有機材料提純裝置是否對有機材料進行提純在內的提純後的有機材料的特性等進行說明。 Hereinafter, the characteristics and the like of the purified organic material including whether or not the organic material is purified by the organic material purifying apparatus of the ionic liquid of the present invention as described above will be described.
1、有機材料的提純裝置及提純方法 1. Purification device and purification method of organic material
第12a圖、第12b圖和第12c圖分別為用於製造水準型有機材料提純裝置的俯視圖、主視圖和側視圖,第13圖為根據第12a圖、第12b圖和第12c圖所示的設計圖來製造的水準型有機材料提純裝置的實物照片。 12a, 12b, and 12c are a plan view, a front view, and a side view, respectively, for fabricating a leveling organic material purifying device, and Fig. 13 is a view according to Figs. 12a, 12b, and 12c. A physical photograph of a leveling organic material purification unit manufactured by a design.
如第12a圖、第12b圖、第12c圖與第13圖所示,水準型有機材料提純裝置包括:昇華部,用於使含有雜質的有機發光二極體用有機材料昇華;捕集部,以與昇華部相連通的方式配置,並使有機材料的昇華氣體和流動的離子液體相接觸來捕集昇華氣體。在這裡,昇華部以與第7圖所示的昇華部相同的概念構成,捕集部以與如第7圖所示的捕集部相同的概念構成,由葉片以外殼(腔室)內的水準軸為中心來旋轉,並使昇華氣體與離子液體相接觸,來使昇華氣體捕集於離子液體並被溶解,從而使昇華氣體再結晶化。 As shown in Fig. 12a, Fig. 12b, Fig. 12c and Fig. 13, the leveling organic material purifying device comprises: a sublimation portion for sublimating the organic light-emitting diode containing impurities with the organic material; the trapping portion, The sublimation gas is trapped in a manner of being in communication with the sublimation portion, and the sublimation gas of the organic material is brought into contact with the flowing ionic liquid to trap the sublimation gas. Here, the sublimation unit is constituted by the same concept as the sublimation unit shown in Fig. 7, and the collection unit is configured in the same manner as the collection unit shown in Fig. 7, and the blade is in the outer casing (chamber). The horizontal axis rotates around the center, and the sublimation gas is brought into contact with the ionic liquid to trap the sublimation gas in the ionic liquid and dissolve, thereby recrystallizing the sublimation gas.
利用如上所述的水準型有機材料提純裝置來執行提純實驗的流程如下。首先,在大氣壓狀態下,將作為提純物件的有機材料裝入昇華部,並在向捕集部注入離子液體之後,以1×10-6Torr對腔室進行抽吸。之後,對離子液體進行加熱,使捕集部的葉片旋轉,將作為提純對象的有機材料加熱至昇華點,並維持規定時間來使提純對象有機材料昇華。這樣,有機材料的昇華氣體飛散,來與沿著葉片流動的離子液體相接觸,並得到捕集及溶解,從而實現再結晶化。若完成這種提純製程,則回收提純後的有機材料,並在分離提純的有機材料和離子液體後,執行對殘留於提純後的有機材料的表面的離子液體進行清洗的過程。 The flow of performing the purification experiment using the level type organic material purifying apparatus as described above is as follows. First, an organic material as a purified article is charged into a sublimation portion under an atmospheric pressure state, and after the ionic liquid is injected into the trap portion, the chamber is suctioned at 1 × 10 -6 Torr. Thereafter, the ionic liquid is heated to rotate the blade of the collecting portion, and the organic material to be purified is heated to the sublimation point for a predetermined period of time to sublimate the organic material for purification. Thus, the sublimation gas of the organic material is scattered to come into contact with the ionic liquid flowing along the blade, and is collected and dissolved, thereby achieving recrystallization. When the purification process is completed, the purified organic material is recovered, and after separating the purified organic material and the ionic liquid, a process of washing the ionic liquid remaining on the surface of the purified organic material is performed.
2、有機材料提純裝置的實驗條件及實驗結果 2. Experimental conditions and experimental results of the organic material purification device
使用1Kg的1-辛基-3-甲基咪唑雙三氟甲磺醯亞 胺(OMIN TFSI,1-Octyl-3-methylimidazolium bis(trifluoromethyl sulfonyl)imide)作為離子液體,使用20g的空穴傳輸層材料(DS 220)作為有機材料。另一方面,在執行提純實驗的過程中,將有機材料的昇華溫度設定為280℃以上,並將離子液體的溫度設定為120℃。而且,將壓力減壓至1×10-6Torr後開始進行昇華,且製程時間執行5小時。 Use 1Kg of 1-octyl-3-methylimidazolium bistrifluoromethanesulfonate An amine (OMIN TFSI, 1-Octyl-3-methylimidazolium bis (trifluoromethyl sulfonyl) imide) was used as an ionic liquid, and 20 g of a hole transport layer material (DS 220) was used as an organic material. On the other hand, in the course of performing the purification experiment, the sublimation temperature of the organic material was set to 280 ° C or higher, and the temperature of the ionic liquid was set to 120 ° C. Further, sublimation was started after the pressure was reduced to 1 × 10 -6 Torr, and the process time was performed for 5 hours.
在如上所述的條件下進行提純實驗的過程中,自開始昇華後經過30分鐘之後起,在離子液體的表面觀察到了浮游物形態的有機材料結晶,之後這種結晶的量增加。即,從圖13的部分放大照片的實驗結果中可知,以再結晶化的方式提純的有機材料在離子液體的表面以浮游物的形態存在。這意味著可利用離子液體對有機材料進行提純。 During the purification experiment under the conditions as described above, crystals of the organic material in the form of a float were observed on the surface of the ionic liquid 30 minutes after the start of sublimation, and then the amount of the crystal was increased. That is, from the experimental results of the partial enlarged photograph of Fig. 13, it is understood that the organic material purified by recrystallization is present in the form of a float on the surface of the ionic liquid. This means that the ionic liquid can be used to purify the organic material.
在結束如上所述的提純製程後,回收提純後的有機材料和離子液體的混合物,並從離子液體分離提純後的有機材料來進行清洗,之後進行各種分析。 After the purification process as described above is completed, the purified mixture of the organic material and the ionic liquid is recovered, and the purified organic material is separated from the ionic liquid for washing, and then various analyses are performed.
3、提純後的有機材料的特性分析 3. Characterization of organic materials after purification
在以下條件下,利用如表1所示的分析設備來分析了提純後的有機材料的特性。 The characteristics of the purified organic material were analyzed under the following conditions using an analytical apparatus as shown in Table 1.
4、Raman PL測定 4, Raman PL determination
測定了進行提純之前和進行提純之後的空穴傳輸層材料基於在大氣環境中暴露的時間的Raman PL特性的變化。這種Raman PL測定用於比較在對空穴傳輸層材料進行提純之間和進行提純之後的基於在大氣環境中暴露的時間的有機材料的穩定性。第14a圖、第14b圖、第14c圖與第14d圖為對通過第13圖所示的水準型有機材料提純裝置來進行提純之前和進行提純之後的空穴傳輸層材料基於在大氣環境中暴露的時間的Raman PL特性變化進行測定的曲線圖。 The change in Raman PL characteristics of the hole transport layer material before and after purification was measured based on the time of exposure in an atmospheric environment. This Raman PL measurement is used to compare the stability of an organic material based on the time of exposure in an atmospheric environment between purification and purification of the hole transport layer material. Figures 14a, 14b, 14c and 14d show the hole transport layer material before and after purification by the leveling organic material purification apparatus shown in Fig. 13 based on exposure to atmospheric conditions. A plot of the measured Raman PL characteristics of the time.
從第14a圖及第14b圖中可知,進行提純之前的空穴傳輸層材料隨著暴露於大氣環境中的時間的經過,峰值(peak)的半高寬(FWHM)的變化幅度達到8cm-1,相反,在第14c圖及第14d圖中所示的進行提純之後的空穴傳輸層材料中,峰值(peak)的半高寬(FWHM)的變化幅度達到0.5cm-1,可確認非常穩定。這意味著利用離子液體提純的有機材料的表面被離子液體的成分保護(passivation)。 It can be seen from Fig. 14a and Fig. 14b that the half-height width (FWHM) of the peak of the hole transport layer material before the purification is exposed to the atmospheric environment reaches 8 cm -1 . On the contrary, in the hole transport layer material after purification as shown in Fig. 14c and Fig. 14d, the variation in the full width at half maximum (FWHM) of the peak reaches 0.5 cm -1 , which is confirmed to be very stable. . This means that the surface of the organic material purified by the ionic liquid is protected by the composition of the ionic liquid.
5、PL測定 5, PL determination
測定了進行提純之前和進行提純之後的空穴傳輸層材料基於在大氣環境中暴露的時間的PL特性的變化。這種PL測定用於比較在對空穴傳輸層材料進行提純之前和進行提純之後的基於在大氣環境中暴露的時間的有機材料的穩定性。第15a圖至第15d圖為對通過第13圖所示的水準型有機材料提純裝置進行提純之前和進行提純之後的空穴傳輸層材料基於在大氣環境中暴露的時間的PL特性變化進行測定的曲線圖。 The change in PL characteristics of the hole transport layer material before and after purification was measured based on the time of exposure in an atmospheric environment. This PL measurement is used to compare the stability of an organic material based on the time of exposure in an atmospheric environment before and after purification of the hole transport layer material. 15a to 15d are graphs for measuring the change in PL characteristics of the hole transport layer material before and after purification by the level-type organic material purifying apparatus shown in Fig. 13 based on the exposure time in the atmospheric environment. Graph.
從第15c圖及第15d圖中可知,提純後的空穴傳輸層材料的發光峰值的位置向短波長(460nm→440nm)側移動,並且,半高寬的值從75nm下降至50nm。這意味著通過提純製程提高了物質的純度。並且,如從圖15a及圖15b中可知,提純之前的空穴傳輸層材料隨著在大氣環境中暴露的時間的經過,峰值位置的變化值達到±5nm,半高寬的變化幅度達到10nm,相反,提純後的空穴傳輸層材料的峰值位置的變化值為±1nm以下,半高寬的變化幅度達到5nm以下。由此可知,利用離子液體提純的有機材料因外部的水分及氧氣所產生的物質的特性變化甚微。這意味著利用離子液體提純的有機材料的表面被離子液體的成分保護。 As can be seen from Fig. 15c and Fig. 15d, the position of the luminescence peak of the hole transport layer material after purification was shifted to the short wavelength (460 nm → 440 nm) side, and the value of the FWHM was decreased from 75 nm to 50 nm. This means that the purity of the material is increased by the purification process. Moreover, as can be seen from FIG. 15a and FIG. 15b, the change of the peak position of the hole transport layer material before purification in the atmospheric environment reaches ±5 nm, and the change width of the full width at half maximum is 10 nm. On the contrary, the change in the peak position of the material for the hole transport layer after purification is ±1 nm or less, and the variation width of the full width at half maximum is 5 nm or less. From this, it can be seen that the organic material purified by the ionic liquid has little change in the characteristics of the substance produced by the external moisture and oxygen. This means that the surface of the organic material purified by the ionic liquid is protected by the composition of the ionic liquid.
6、掃描電子顯微鏡測定 6, scanning electron microscopy
測定了進行提純之前和進行提純之後的空穴傳 輸層材料基於在大氣環境中暴露的時間的表面形狀的變化。這種PL測定用於比較在對空穴傳輸層材料進行提純之前和進行提純之後的基於在大氣環境中暴露的時間的有機材料的穩定性。第16a圖、第16b圖、第16c圖與第16d圖為對通過第13圖所示的水準型有機材料提純裝置進行提純之前和進行提純之後的空穴傳輸層材料基於在大氣環境下暴露的時間的表面形狀的變化進行拍攝的掃描電子顯微鏡(SEM,×1k)照片。 The hole pass before and after purification was measured. The layer material is based on changes in surface shape over time exposed in the atmosphere. This PL measurement is used to compare the stability of an organic material based on the time of exposure in an atmospheric environment before and after purification of the hole transport layer material. Figs. 16a, 16b, 16c and 16d are diagrams showing the hole transport layer material exposed to the atmosphere before and after purification by the level-type organic material purifying apparatus shown in Fig. 13. A change in the surface shape of the time was taken by scanning electron microscopy (SEM, ×1k) photographs.
在進行提純之前的空穴傳輸層材料為合成之後的物質,純度為98.6%左右,從第16a圖、第16b圖、第16c圖與第16d中可知,在表面形狀方面未觀察到特殊的特徵。但在通過本發明的水準型有機材料提純裝置進行提純的空穴傳輸層材料中,觀察到球狀的結晶粒。這種結晶粒的大小具有5μm的非常均勻的尺寸。另一方面,未觀察到基於時間的表面形狀的變化。 The material of the hole transport layer before the purification is a substance after the synthesis, and the purity is about 98.6%. From the 16th, 16b, 16c, and 16d, no special characteristics are observed in the surface shape. . However, in the hole transport layer material purified by the level-type organic material purifying apparatus of the present invention, spherical crystal grains were observed. The size of such crystal grains has a very uniform size of 5 μm. On the other hand, no change in the shape of the surface based on time was observed.
7、X射線光電子能譜測定 7. X-ray photoelectron spectroscopy
通過X射線光電子能譜測定來調查了利用本發明的水準型有機材料提純裝置提純的有機材料的特徵。第17圖為根據通過第13圖所示的水準型有機材料提純裝置提純的有機材料的特徵的X射線光電子能譜的曲線圖。 The characteristics of the organic material purified by the leveling organic material purifying apparatus of the present invention were investigated by X-ray photoelectron spectroscopy. Fig. 17 is a graph showing the X-ray photoelectron spectroscopy of the characteristics of the organic material purified by the level-type organic material purifying apparatus shown in Fig. 13.
從第17圖中可知,檢測出源於有機材料的提純所使用的離子液體的陰離子成分的氟(F)元素、硫(S)元 素。這作為利用離子液體的有機材料提純方法的固有結果,呈現出陰離子及陽離子在提純製程中實現再結晶化的有機材料的表面在分子水準下進行化學結合。因此,可知提純後的有機材料的表面被離子液體、源於離子液體的成分(構成離子液體的成分)或構成離子液體的粒子保護。尤其,可知提純後的有機材料的表面被化學結合的單一分子層的陰離子保護。最終,隨著提純後的有機材料的表面被保護,如上所述,基於在大氣環境中暴露的時間的提純後的有機材料的特性得到穩定的維持。這種特徵,即,檢測出極少量的源於所使用的離子液體的特性成分的元素為以利用離子液體的提純方法來提純的有機材料的固有的特徵,通過調查這種特徵,可判斷物件有機材料是否為採用利用離子液體的提純方法來提純的物件物。因此,本發明包含提供具有這種提純物的特徵的有機材料。 As is apparent from Fig. 17, the fluorine (F) element and the sulfur (S) element of the anion component of the ionic liquid used for the purification of the organic material are detected. Prime. This is an intrinsic result of an organic material purification method using an ionic liquid, and exhibits chemical bonding of the surface of an organic material which recrystallizes anions and cations in a purification process at a molecular level. Therefore, it is understood that the surface of the purified organic material is protected by the ionic liquid, the component derived from the ionic liquid (the component constituting the ionic liquid), or the particles constituting the ionic liquid. In particular, it is known that the surface of the purified organic material is protected by an anion of a chemically bonded single molecular layer. Finally, as the surface of the purified organic material is protected, as described above, the properties of the purified organic material based on the exposure time in the atmospheric environment are stably maintained. This feature, that is, the detection of a very small amount of an element derived from the characteristic component of the ionic liquid to be used is an inherent characteristic of an organic material purified by a purification method using an ionic liquid, and by investigating such a feature, the object can be judged. Whether the organic material is an object purified by a purification method using an ionic liquid. Accordingly, the present invention encompasses organic materials that provide features having such a purification.
但是,在有機發光二極體面板製程方面,若源於離子液體的氟成分、硫成分混入元件當中,則有可能對元件特性產生不利影響。因此,在進行用於製造元件的蒸鍍工製程之前,有必要去除源於保護有機材料的表面的離子液體的氟成分、硫成分。 However, in the process of the organic light-emitting diode panel, if a fluorine component or a sulfur component derived from an ionic liquid is mixed into the element, there is a possibility that the element characteristics are adversely affected. Therefore, it is necessary to remove the fluorine component and the sulfur component of the ionic liquid derived from the surface protecting the organic material before performing the vapor deposition process for manufacturing the component.
因此,本發明人進行實驗之後,確認了只要通過氬離子蝕刻(Ar ion etching)或通過100℃溫度以上的熱處理,就可以完全去除源於保護有機材料的表面的離子液體的 成分。若這種雜質存在於有機材料的內部,則無法通過這種熱處理或簡單的氬離子蝕刻等的方法來去除雜質,因而上述結果證明僅在提純後的有機材料的表面存在極少量的源於離子液體的成分。 Therefore, after conducting experiments, the inventors confirmed that the ionic liquid derived from the surface protecting the organic material can be completely removed by argon ion etching or heat treatment at a temperature of 100 ° C or higher. ingredient. If such an impurity is present inside the organic material, impurities cannot be removed by such heat treatment or simple argon ion etching or the like, and thus the above results prove that only a small amount of ions originating from the surface of the purified organic material exist. The composition of the liquid.
第18圖為在120℃的溫度下對提純後的有機材料進行1分鐘的熱處理後以X射線光電子能譜來對表面結構進行分析的曲線圖。從第18圖中可知,在緣于氟成分、硫成分的位置檢測出非常細微的峰值,這意味著通過熱處理來去除存在於提純的有機材料的表面的大部分的氟成分、硫成分。由此,確認了可以在元件製程中投入提純的有機材料之前,可以在流通路徑中穩定地操作提純後的有機材料,並確認了在進行元件製程之前,可通過適當的預處理來完全去除源於保護有機材料的表面的離子液體的成分,因而在元件製程中不產生任何不利影響。 Fig. 18 is a graph showing the surface structure analysis by X-ray photoelectron spectroscopy after heat treatment of the purified organic material for 1 minute at a temperature of 120 °C. As is clear from Fig. 18, a very fine peak is detected at the position of the fluorine component and the sulfur component, which means that most of the fluorine component and the sulfur component present on the surface of the purified organic material are removed by heat treatment. Thus, it was confirmed that the purified organic material can be stably operated in the flow path before the purification of the organic material in the component process, and it is confirmed that the source can be completely removed by appropriate pretreatment before the component process is performed. The composition of the ionic liquid that protects the surface of the organic material does not cause any adverse effects in the component process.
另一方面,在上述實施例及實驗例中,確認了隨著借助離子液體對含有雜質的有機發光二極體用有機材料進行提純,而提純後的有機材料的表面被離子液體、源於離子液體的成分或構成離子液體的離子保護。但本發明還可通過在借助現有的昇華提純方法等來提純的有機材料的表面塗敷離子液體,從而使提純後的有機材料的表面被離子液體、源於離子液體的成分或構成離子液體的離子保護。此時,將離子液體塗敷於提純後的有機材料的表面的方法可使用普通的 噴射塗敷、浸漬塗敷等多種方法。 On the other hand, in the above examples and experimental examples, it was confirmed that the surface of the organic material purified by the organic material for the organic light-emitting diode containing impurities by the ionic liquid is ionic liquid, derived from ions. The composition of the liquid or the ionic protection of the ionic liquid. However, the present invention can also apply an ionic liquid to the surface of an organic material purified by an existing sublimation purification method or the like, so that the surface of the purified organic material is made of an ionic liquid, an ionic liquid-derived component, or an ionic liquid. Ion protection. At this time, the method of applying the ionic liquid to the surface of the purified organic material can be carried out using ordinary Various methods such as spray coating, dip coating, and the like.
綜上所述,本發明所揭露的有機材料中,為了實現有機材料的高純度化,利用離子液體對有機材料進行提純,或者在提純後的有機材料的表面塗敷離子液體,來在有機材料的表面形成保護層,從而具有在大氣環境下也可便於使提純的有機材料穩定的優點。即,本發明可防止提純後的有機材料受水分的影響,因此具有非常便於在大氣環境下對有機材料進行操作的優點。此外,本發明的有機材料可通過熱處理或使能量粒子相碰撞的方法來完全去除源於保護有機材料的表面的離子液體的成分,因而具有不會對元件製程產生任何不利影響的優點。 In summary, in the organic material disclosed in the present invention, in order to achieve high purity of the organic material, the organic material is purified by the ionic liquid, or the ionic liquid is coated on the surface of the purified organic material to be used in the organic material. The surface forms a protective layer, thereby having the advantage that it is also convenient to stabilize the purified organic material in an atmospheric environment. That is, the present invention can prevent the organic material after purification from being affected by moisture, and therefore has an advantage that it is very convenient to operate the organic material in an atmospheric environment. Further, the organic material of the present invention can completely remove the components of the ionic liquid derived from the surface protecting the organic material by heat treatment or collision of the energy particles, and thus has an advantage that it does not adversely affect the component process.
以上,與附圖一併說明了本發明的具有保護層的有機材料及用於生成這種有機材料的有機材料提純裝置的技術事項,但這屬於以例示性的方式說明本發明的最優選的實施例。因此,本發明並不局限於以上所記載的實施例,在不脫離本發明的思想及範圍的情況下,可對本發明進行多種修改及變形,這對於本發明所屬技術領域的普通技術人員而言是顯而易見的,因此,這種變形例或修改例也屬於本發明的發明要求保護範圍。雖然本發明以前述之較佳實施例揭露如上,然其並非用以限定本發明,任何熟習相像技藝者,在不脫離本發明之精神和範圍內,當可作些許之更動與潤飾,因此本發明之專利保護範圍須視本說明書所附之申請專利範圍 所界定者為準。 The technical matters of the organic material having a protective layer and the organic material purifying apparatus for producing such an organic material of the present invention are described above together with the accompanying drawings, but this is to exemplify the most preferred embodiment of the present invention. Example. Therefore, the present invention is not limited to the embodiments described above, and various modifications and changes can be made to the present invention without departing from the spirit and scope of the invention. It is obvious that such modifications or modifications are also within the scope of the invention as claimed. While the present invention has been described above in terms of the preferred embodiments thereof, it is not intended to limit the invention, and the invention may be modified and modified without departing from the spirit and scope of the invention. The scope of patent protection of the invention shall be subject to the scope of patent application attached to this specification. The definition is final.
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