Liquid-Phase Epitaxy Effective Encapsulation of Lanthanide

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Liquid-Phase Epitaxy Effective Encapsulation of Lanthanide Coordination Compounds into MOF Film with Homogeneous and Tunable White-Light Emission Zhi-Gang Gu, Zheng Chen, Wen-Qiang Fu, Fei Wang, and Jian Zhang ACS Appl. Mater. Interfaces, Just Accepted Manuscript • DOI: 10.1021/acsami.5b09975 • Publication Date (Web): 07 Dec 2015 Downloaded from http://pubs.acs.org on December 8, 2015

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ACS Applied Materials & Interfaces

Liquid-Phase

Epitaxy

Effective

Encapsulation

of

Lanthanide

Coordination Compounds into MOF Film with Homogeneous and Tunable White-Light Emission Zhi-Gang Gu*†, Zheng Chen‡, Wen-Qiang Fu §, Fei Wang † and Jian Zhang *† †

State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of

Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002, P.R. China. ‡

College of Materials Science and Engineering, Fujian Normal University, Fuzhou, Fujian

350007, P.R. China. §

College of Chemistry, Fuzhou University, Fuzhou, Fujian 350108, PR China

Keywords: liquid phase epitaxy, MOF thin film, lanthanide coordination compounds, encapsulation, tunable white-light emission ABSTRACT: As a new family of hybrid inorganic-organic materials with large porosity, metalorganic frameworks (MOFs) have received attractive attention recently on encapsulating functional guest species. Although the encapsulation of luminescent guest into bulk MOFs can tune luminescent property, the powder composite materials are limited to the application in optical sensors and devices. In present work, we use a modified liquid-phase epitaxial (LPE) pump method for the fabrication of lanthanide coordination compounds (LCCs) encapsulated MOF thin film on substrate with high encapsulation efficiency. The resultant composite film reveals an oriented and homogenous composite film, which can be obtained a white light emission by tuning the LCCs of red, blue and green emission. This strategy may open new perspectives for developing high encapsulation efficiency, oriented and homogenous solid-state lighting composite films in the application of optical sensors and devices.

INTRODUCTION

ACS Paragon Plus Environment

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The establishment for encapsulating with guest is a crucial step for many applications of porous materials. As a new family of hybrid inorganic-organic porous materials, metal-organic frameworks (MOFs) have received attractive attention recently because of the abundant flexible pores of MOFs offer large loading capacity for functional guest species providing the host matrices with enhanced or new properties.1-4 Up to now, some luminescent guests (e.g. quantum dot, dye molecules, lanthanide ions) have been encapsulated into the pores of MOFs with emission property by using on-pot hydrothermal method or immersing the guest solutions.5-10 However, the compositions of the materials obtained with these methods are not easy to control and the methods are limited to encapsulate guest with high efficiency. On another hand, thin film materials have been used widely in semiconductor devices, solar cells, transistors, light emitting diodes, light crystal displays, smart windows, chips as well as temperature and gas sensors.11-13 The encapsulation of luminescent guest into bulk MOFs with powder materials are not popular for the applications in optical sensors and devices because of their high scattering and non-uniform thickness. In recent years, thin films of MOFs have been increasingly investigated due to the enhancement of active interface with large surface areas.14-19 Liquid-phase epitaxy (LPE) layer-by-layer procedure has proven to be an efficient method to control the growth orientations, thickness and homogeneity of MOF thin films.20-23 In particular, the well-defined layer-by-layer assembly fashion might allow us to encapsulate the presynthesized guest into MOFs without disrupting the growth of the MOF structures. Lanthanide coordination compounds (LCCs) represent fascinating and tunable luminescent light emission properties correlated to lanthanide and organic ligands functionality, which are supposed to be promising optical materials.24-28 However, in order to apply these materials for devices and sensors, preparing LCCs with ordered and homogeneous provide a good opportunity for the the applications of sensors and devices. A convenient method is encapsulating LCCs with strong luminescent property into crystalline MOFs with ordered micropores. Although there have been a number of reports on preparation of luminescent MOFs and tuning luminescence properties of these materials, the efforts in design and synthesis of MOFs with good luminescent property are limited.29,

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As a porous MOFs, very few scientists pay attention on the

encapsulation of luminescent guest into the pores of MOF. The present encapsulation methods are used by on-pot hydrothermal method or immersing the guest solutions. However, the preparation procedure of one-pot hydrothermal method is hard to control while the he guest


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candidates are limited to window size of MOF and surface barrier on MOF. Herein, we use a modified liquid-phase epitaxial (LPE) pump method for the fabrication of luminescent guest encapsulated MOF thin film (scheme 1) since it can offer the chance to incorporate large, foreign species into ordered and homogenous pores. This new strategy can achieve high-efficiency luminescent guest encapsulating. The LCCs Ln(pdc)3 (H2pdc = pyridine-2,6-dicarboxylic acid, Ln = Eu, Tb and Gd)31 were selected as the luminescent guest species, which are well known for their advantages including (i) high photoluminescent efficiency; (ii) easy to prepare a large amount using hydrothermal method; (iii) easy to tune the color light emission. On another side, 3-D MOF HKUST-1 (Cu3BTC2, H3BTC = benzene-1,3,5-tricarboxylic acid)32 was chosen as the host framework, containing large numbers of ordered micropores for guest loading. Since Cu(II) ions with unpaired electrons has luminescence quencher effect usually when it coordinate to organic ligands,33 a Cu(II) based MOF HKUST-1 host framework has no luminescence property, which provide abundant pores for guest encapsulation without influencing the luminescence of guest. Therefore, the pure and mixed Ln(pdc)3 can be encapsulated into HKUST-1 to form composite film with different color light emission (particularly white light emission) via modified LPE method. The color luminescence emission of obtained composite films would be a promising strategy in the development of RGB-luminescent sensors and devices.

Scheme 1. The modified LPE pump method for growth of Ln(pdc)3 encapsulated MOFs thin films on functionalized substrates. The preparation is done by repeated immersion cycles in the metal precursor, organic ligand and guest solutions subsequently. (Note: There is a solvent rinsing for each step)

EXPERIMENTAL SECTION


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All the reagents and solvents employed were commercially available and were used as received without further purification. The quartz glass substrates were treated with a mixture of concentrated sulfuric acid and hydrogen peroxide (30 %) with a volume ratio 3:1 at 80 °C for 30 minutes and then cleaned with deionized water and dried under nitrogen flux for the next preparation. The samples grown on functionalized Au substrate were characterized with infrared reflection absorption spectroscopy (IRRAS). IRRAS data were recorded using a Bruker Vertex 70 FTIR spectrometer with 2 cm-1 resolution at an angle of incidence of 80° relative to the surface normal. Powder X-ray diffraction (PXRD) analysis was performed on a MiniFlex2 X-ray diffractometer using Cu-Kα radiation (λ = 0.1542 nm) in the 2θ range of 4–20° with a scanning rate of 0.5° min−1. Transmission electron microscope (TEM) images and EDS recorded for Ln(pdc)3 encapsulated HKUST-1 thin films were used JEM-2010F. Scanning electron microscope (SEM) images for the morphology of thin films were measured by JSM6700. Inductively coupled plasma spectroscopy (ICP) was performed for the ratio of Eu, Tb, Gd and Cu elements in the mixed Ln(pdc)3@HKUST-1 thin film. Fluorescence spectra for the solid samples were performed on an Edinburgh Analytical instrument FLS920. RESULTS AND DISCUSSION The guest species coordination compounds (CH3NH2)3Ln(pdc)3 (Ln = Eu, Tb and Gd; pdc = pyridine-2,6-dicarboxylate) are strong luminescent materials with red (Ln = Eu), green (Ln = Tb) and blue (Ln = Gd) light emission, which also can be obtained a white light emission by tuning the compositions of red, blue and green emission. In this work, the mixture of Ln(NO3)3·6H2O (0.25 mmol, Ln = Eu, Tb and Gd), pyridine-2,6-dicarboxylic acid (H2pdc 0.75 mmol) and dimethylamine (0.75 mmol) were formed by hydrothermal method referring to the reported work as shown in the Figure 1c, which is identical to the simulated XRD of the previous work31, 34. In the structure, a saturation of the metal coordination sphere with the anticipated N3O6 chromophore, giving a distorted tricapped trigonal prism as shown in Figure 1a. For obtaining the powder LCCs Ln(pdc)3 with the white color, the mixtures of Eu(pdc)3, Tb(pdc)3 and Gd(pdc)3 with tunable proportion were mixed to form the resulting mixed Ln(pdc)3. In brief, the mixture of crystal powder Eu(pdc)3, Tb(pdc)3 and Gd(pdc)3 with different composition was dissolved and recrystallized powder mixed Ln complex EuaTbbGd1-a-b(pdc)3 (see the powder XRD in Figure 2c, a and b are the components of Eu and Tb, respectively). HKUST-1


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(also called Cu3BTC2, H3BTC = benzene-1,3,5-tricarboxylic acid), a standard 3D MOF was chosen as the host framework, which has high porosity to encapsulate the guest LCCs in present work.

Figure 1. (a) Perspective view of Ln(pdc)3 (Ln= Eu, Tb and Gd). Carbon: white, oxygen: red, nitrogen: blue, Ln: green. Hydrogen atoms are omitted for clarity; (b) the Ln(pdc)3 powder

showed individual red (Ln = Eu), green (Ln = Tb) and blue (Ln = Tb) and the mixed Ln(pdc)3 with appropriate ratio showed white color under radiation of ultraviolet illumination; the powder XRD of Ln(pdc)3 (Ln= Eu, Tb and Gd) powder and the mixed Ln(pdc)3 with white light emission. Since LPE approach can provide a perfect way to load much broader range of guests into MOF thin film. In this work, the modified pump method35,

36

setup was applied for the

growth of Ln(pbd)3@MOF thin film on the substrates. In addition, as a highly symmetric structural (crystallographic space group: Fm-3m) MOF, HKUST-1 with Cu(II) paddle-wheel units is easily prepared using LPE layer by layer approach.37 Due to the preparation of all the guest species encapsulated HKUST-1 film are similar, only the preparation of Eu(pdc)3@HKUST-1 film was described for clarity here. In brief, the Cu(OAc)2, H3BTC,


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Eu(pdc)3 (drops of water for dissolution in ethanol) and pure ethanol solutions were injected into the reaction cell with functionalized substrate sequentially as shown in scheme 1. A thin film was obtained after repeating 100 cycles, which is named Eu(pdc)3@HKUST-1 film. As examined by surface X-ray diffraction in an out of plane mode, XRD peaks of all the samples at 6.8, 13.6, 11.6 and 17.5º are in accord with the simulated XRD peaks at (200), (400), (222) and (333) of HKUST-1, indicating that the framework of thin film is unchanged and grown along [100] and [111] orientations on the present functionalized quartz glasses (Figure 2b). Compare to the simulated powder XRD of HKUST-1, the relative intensities of (200)/(400) were decreased in all the guest load HKUST-1 samples, which can be attributed to changes in the structure form factor with a partial change from a F- to an I-type lattice.38 We can demonstrate the luminescent guest was loaded in the pores of HKUST-1.39, 40 To study the IR spectra of Ln(pdc)3@HKUST-1 films, the film sample grown on SAM functionalized Au substrate for measurement. The IR absorbance bands at 1433, 1560 and 1614 cm-1 are ascribed to C-O vibrations of Ln(pdc)3, showing the luminescent guest encapsulating into HKUST-1 successfully. Photographs of the Ln(pdc)3@HKUST-1 film sample under radiation at 365 nm (ultraviolet lamp) are given in Figure 3a~c, showing the red for Eu(pdc)3@HKUST-1 film, green for Tb(pdc)3@HKUST-1 film and blue for Gd(pdc)3@HKUST-1 film, respectively. The intense luminescence of Ln(pcd)3@HKUST-1 films show that the luminescence of composite films would not be effected by Cu-MOF HKUST-1. Because there is no coordination interaction between host framework HKUST-1 and guest LCCs, the Cu(II) only influence luminescence on the framework HKUST-1 rather than guest LCCs.


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Figure 2. (a) schematic presentation of in situ layer-by-layer growth of Ln(pdc)3 encapsulated HKUST-1 thin film using modified LPE pump method; (b) the out plane XRD Ln(pdc)3@HKUST-1 film (Ln=Eu, Tb, Tb) and mixed Ln(pdc)3@HKUST-1 film with white light emission; (c) infrared spectrum of Eu(pdc)3@HKUST-1 film.

To study the optical properties of Ln(pdc)3@HKUST-1 films, the film sample grown on quartz glass for photoluminescent measurement. With excitation at 396 nm, the solid state photoluminescent (PL) spectra at room temperature (Figure 4a) exhibits Eu(pdc)3@HKUST-1 film an intense red emission with peaks located at 593, 615, 650, and 693 nm that can be attributed to the 5

D0→7FJ (J = 1-4) transitions of the Eu3+ ion. The emission spectra of Tb(pdc)3@HKUST-1 film

show green-luminescence with mission bands at 491, 543, 583, 615, and 650 nm with excitation


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at 322 nm, assigned to the

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D4→7FJ (J =6-2) transitions (Figure 4b). The film of

Gd(pdc)3@HKUST-1 displays an ligand-centered blue emission at 418 nm upon excitation at 315 nm (Figure 4c). These luminescent spectra of Ln(pdc)3@HKUST-1 films are similar as the spectra of powder Ln(pdc)3 (Figure S1). These phenomena suggest that the intramolecular energy transfer from ligand to Tb3+/Eu3+ is effective when the Tb3+/Eu3+ coordinates with the pdc ligand and the pdc ligand exhibits π→π* transitions in Gd3+ coordination, indicating that the optical properties of present composite films mainly were influenced by guest Ln(pdc)3 rather than host framework HKSUT-1. The organic linker BTC and metal ion Cu2+ in the host framework rarely influence the luminescence property of composite film. The Ln(pdc)3@HKUST-1 films show the visible red, green and blue light with CIE (Commission International de L’Eclairage) chromaticity coordinates of (0.63, 0.33), (0.29, 0.46) and (0.19, 0.16) in Figure 4e, respectively. The lifetimes (τ) and quantum yields of are 1.81 ms, 1.56 ms, 2.19 µs and 61.60%, 26.65%, 14.53, respectively (see Figure S9-S14 and Table S1 in the supporting information). Compare to the lifetimes between Ln(pdc)3 powder and Ln(pdc)3@HKUST-1 films (see the Table S1), Ln(pdc)3@HKUST-1 films have longer lifetimes showed that the luminescent lifetime of luminescent guest can be enhanced after encapsulating into porous MOFs.

Figure 3. Photographs of Ln(pdc)3@HKUST-1 film and mixed Ln(pdc)3@HKUST-1 film on quartz glasses prepared by using a modified LPE pump method (a~d), the photographs were collected under


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radiation

of

ultraviolet illumination

(365

nm);

(e)

surface

morphology of

the

obtained

Eu(pdc)3@HKUST-1 film with different amplifications.

The Eu(pdc)3, Tb(pdc)3 and Gd(pdc)3 LCCs can ideally be composed of three RGB primary colors for tuning different colors. In particular, white light emission gives an opportunity for their applications of white light emitting diodes (WLED). The films materials with white light emission can be a promising candidate for their diverse devices and sensors in WLED, which can be used in application of lighting and display. The white light emission should ideally be composed of red, green and blue (RGB) primary colors and cover the whole visible range from 400 to 700 nm. Here, we realized white-light emission by precise control of the Gd/Eu/Tb proportion in the powder Ln(pdc)3 materials. For the purpose of white light emission film, the mixed Ln(pdc)3 with white light emission was prepared and chosen as the guest for encapsulating into HKUST-1 film on quartz glass using present modified LPE pump method. The obtained sample (namely white@HKUST-1 film) with oriented and homogenous film (Figure 3e) produced a white color under radiation of ultraviolet illumination as shown in Figure 3d. With excitation at 291 nm, the photoluminescent emission spectra shows all expectant typical emission bands at 418, 492, 543, 583, 615, and 650 nm (Figure 4d) with quantum yield of 46.50%, assigned to the all the transitions from Ln(pdc)3 (Ln=Eu, Tb and Gd). The corresponding CIE chromaticity coordinate (0.37, 0.38) of white@HKUST-1 film locates in the white region in the CIE diagram, which is close to the coordinate for pure white-light (0.33, 0.33) (Figure 4e). Furthermore, A white LED was fabricated by Ln(pdc)3 (Ln=Eu, Tb and Gd) encapsulated HKUST-1 with a ultraviolet LED chip with 50 lm/W. The strong white emission from the LED could be observed under 350 mA forward bias current, as shown in Figure S8. The related colour parameters of colour-rendering index (CRI) and correlated colour temperature (CCT) values were estimated to be 82.8 and 5880 K, respectively. For define the component of white@HKUST-1, the molar ratios of Gd3+/Eu3+/Tb3+ exclusively was confirmed by inductively coupled plasma spectroscopy (ICP) and shown the component ratio is 0.0131/0.157/0.830. Furthermore, the ratio of Cu2+/Ln3+ is 12.033, which is very closed to the simulation ratio 12,39 demonstrating there is a nearly fully encapsulation in the big pores (1.66 nm) of HKUST-1 (see the model in Figure S2). As compared to Ln(pdc)3 powder luminescent materials, such as LCCs loaded MOFs film exhibits luminescent films with controllable layer thickness, homogenous, ordered and high-efficiency encapsulation when the Ln(pdc)3 guest locates in the ordered


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micropore of HKUST-1.

Figure 4. Solid-state photoluminescence (PL) emission spectra of the Eu(pdc)3@HKUST-1, Tb(pdc)3@HKUST-1, Gd(pdc)3@HKUST-1 film on functionalized Au substrate with red (a), green (b) and blue (c) light emission; (d) the The fluorescence spectrum the mixed Ln(pdc)3@HKUST-1 film with white light emission; (e) The CIE chromaticity coordinates diagram of the Ln(pdc)3@HKUST-1

film with red, gree, blue light emission and the mixed Ln(pdc)3@HKUST-1 film with white light emission.

CONCLUSION In summary, we have illustrated a new encapsulation strategy for the design of luminescent lanthanide coordination compounds (LCCs) loaded MOFs composite films on the substrates. By using a modified LPE pump method, the Ln(pdc)3 LCCs (Ln=Eu, Tb and Gd) were loaded into the pores of MOFs HKUST-1 film to form the composite films with (RGB) primary colors. In particular, using the same approach, the mixture of Ln(pdc)3 (Ln=Eu, Tb and Gd) with appropriate proportion were encapsulated into HKUST-1, resulting in a film of white light emission. The host framework in present strategy was rarely involved in tuning the luminesce


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property, however, the oriented, homogenous MOF film prepared by modified LPE fashion provided a high-efficiency, homogenous encapsulation of luminescent guest in the pores of MOF and controllable layer thickness of composite film. This in situ LPE encapsulation in a wellcontrolled and high-efficiency strategy, we believe, it opens a new perspective for the development of high performance white light emission devices and sensors with homogenous, ordered and controllable thickness and active interface.

ASSOCIATED CONTENT Supporting Information. Experimental and characterization details; additional figures and images; XRD patterns; luminescence lifetimes; TGA and and IR, This material is available free of charge via the Internet at http://pubs.acs.org.

AUTHOR INFORMATION Corresponding Author Zhi-Gang Gu: [email protected]; Jian Zhang: [email protected]; Author Contributions The manuscript was written through contributions of all authors. All authors have given approval to the final version of the manuscript. Notes The authors declare no competing financial interests. ACKNOWLEDGMENT This work is supported by the 973 program (2012CB821705) and NSFC (21425102, 91222105 and 21221001). REFERENCES


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Table of Contents Graphic and Synopsis

Graphical Abstract: We use a modified liquid-phase epitaxial (LPE) pump method for the fabrication of lanthanide coordination compounds (LCCs) encapsulated MOF thin film on substrate, and this strategy may open new perspectives for developing high encapsulation efficiency, oriented and homogenous solid-state lighting composite films in the application of optical sensors and devices.


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Liquid-Phase Epitaxy Effective Encapsulation of Lanthanide

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