Fabrication of a Homogeneous, Integrated, and Compact Film of

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Fabrication of a Homogeneous, Integrated, and Compact Film of Organic−Inorganic Hybrid Ni(en)3Ag2I4 with Near-Infrared Absorbance and Semiconducting Features Tian-Yu Chen,†,‡ Lei Shi,† Hao Yang,†,‡ Xiao-Ming Ren,*,†,‡ Chen Xiao,†,‡ and Wanqin Jin*,† †

State Key Laboratory of Material-Oriented Chemical Engineering, Nanjing Tech University, Nanjing 210009, P. R. China College of Chemistry and Molecular Engineering, Nanjing Tech University, Nanjing 211816, P. R. China

‡

S Supporting Information *

ABSTRACT: The organic−inorganic hybrid crystal Ni(en)3Ag2I4 (where en represents 1,2-ethylenediamine) crystallizes in hexagonal space group P63, in which the AgI43− tetrahedra connect into a diamondlike inorganic framework via sharing of the vertex and the Ni(en)32+ octahedra fill in the pores of the framework. UV−vis−near-IR (NIR) spectroscopy disclosed that this hybrid shows intense NIR absorbance centered at ca. 870 nm, and the variable-temperature conductivity measurement revealed that the hybrid is a semiconductor with Ea = 0.46 eV. The electronic band structure of Ni(en)3Ag2I4 was calculated using the density functional theory method, indicating that the NIR absorbance arises from d-d transition within the Ni2+ cation of Ni(en)32+. The homogeneous, compact, and transparent crystalline film of Ni(en)3Ag2I4 was fabricated via a secondary seed growth strategy, which has promising application in NIR devices.

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INTRODUCTION Near-infrared (NIR; 750−1500 nm) light absorbance has played an increasingly important role in addressing optical issues1,2 ranging from NIR shielding,3 solar filters,4 invisible inks,5 laser-welding,6 photovoltaics,7−9 and optical storage1 materials to photothermal therapy10,11 and photothermal control of the gelation for drug deliveries.12 NIR materials can roughly be divided into two groups:1 inorganic materials including metal oxides,4,13,14 noble-metal particles,15 and semiconductor nanocrystals8 and organic materials including metal complexes,16,17 extended π-conjugated chromophores,18 donor−acceptor charge-transfer chromophores,19,20 and carbon-based particles21,22 as well. Recently, organic−inorganic hybrid NIR absorption materials have been engaging scientists’ attention23 because they probably have the capability of merging the advantages of organic components (straightforward synthetic approach, easily tailored molecular structure, and functional properties) with those of a robust inorganic network (chemical, thermal, and mechanical stabilities). In this paper, we report on the fabrication of a uniform, compact, and transparent film of the organic−inorganic hybrid crystal Ni(en)3Ag2I4 (where en represents 1,2-ethylenediamine) via a secondary seed growth strategy. We also present an investigation of the NIR absorbance, temperature-dependent © XXXX American Chemical Society

conductivity, and electronic band structure analysis for Ni(en)3Ag2I4.

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EXPERIMENTAL SECTION

Materials and Reagents. Water was distilled and deionized with a Milli-Q filtering system, and other solvents [absolute ethanol and N,Ndimethylformamide (DMF)] and chemicals, including KI, AgNO3, Ni(NO3)2·6H2O, 1,2-ethylenediamine (en), and (3-mercaptopropyl)trimethoxysilane (MPTS), are commercially available and were used without further purification. Preparation of a Polycrystalline Sample of Ni(en)3Ag2I4. A polycrystalline sample of Ni(en)3Ag2I4 was prepared following the published procedure24,25 and confirmed by a powder X-ray diffraction (PXRD) technique. Preparation of the Mother Liquor for Growth of a Ni(en)3Ag2I4 Film. A saturated solution of potassium iodide was prepared by dissolving KI (7.6 g) in 20 mL of DMF at ambient temperature and filtered by suction to remove the insoluble solids (this solution was labeled as solution-I). AgNO3 (0.865 g) was dissolved in 10 mL of DMF at ambient temperature to give solution-II. Solution-I and solution-II were mixed with stirring for 30 min, and then 50 mL of DMF was added into the mixed solution to give solution-III with a concentration of 0.1 M Ag+ ions. Received: October 21, 2015

A

DOI: 10.1021/acs.inorgchem.5b02439 Inorg. Chem. XXXX, XXX, XXX−XXX

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and the beaker placed in an oven was first heated from ambient temperature to 80 and 100 °C and then cooled sequentially, which was controlled using a programmed heating−cooling process during the growth of a Ni(en)3Ag2I4 film. The quartz glass with a Ni(en)3Ag2I4 film was taken out from the mother liquor upon cooling to ambient temperature, washed using DMF and ethanol in sequence, and dried in air for other measurements. Physical Measurements. PXRD data were collected on a Bruker D8 diffractometer with Cu Kα radiation (λ = 1.5418 Å) at ambient temperature. Temperature-dependent PXRD measurements were recorded on a Shimadzu XRD-6100 diffractometer operating with a Cu Kα radiation source (λ = 1.5418 Å) in the temperature range from 20 to 190 °C (293−463 K) with voltage = 40.0 kV and current = 30.0 mA (scan 2θ range = 8.0−60.0°; scan speed = 2.0 °C·min−1). Thermogravimetric (TG) analysis was performed using a TGA Q500 instrument, and the sample was held in a platinum pan under a nitrogen flow at a rate of 40 mL·min−1 and heated at a ramping rate of 10 °C·min−1 from 25 to 600 °C. UV−vis−NIR spectroscopy was recorded on a Shimadzu UV-2401TC spectrophotometer. The morphologies of the Ni(en)3Ag2I4 film on the quartz glass substrate and the submicron crystals were observed using field-emission scanning electron microscopy (FESEM; Hitachi S-4800). The direct-current (dc) conductivity was investigated using a CHI 660D electrochemical workstation by a two-probe method. The crystalline sample was milled into a fine powder and then made into a pellet, under a pressure of ca. 40 MPa, with 0.204 cm thickness and 0.8 cm diameter. The measurement was performed in the temperature range of 20−160 °C (293−433 K) because the sample of Ni(en)3Ag2I4 is thermally stable below200 °C. Density Functional Theory (DFT) Calculations for Electronic Band Structures. Electronic band structure calculations were performed using the Cambridge Sequential Total Energy Package (CASTEP) program26,27 for Ni(en)3Ag2I4 on the nonmodelized crystal structure obtained from single-crystal X-ray structure analysis. The electronic band structures of both Ni(en)3Ag2I4 and the isostructural Zn(en)3Ag2I424 were calculated, respectively. The generalized gradient approximations of the Perdew−Burke−Ernzerhof28 potentials have

A solution of nickel nitrate was made by dissolving Ni(NO3)2 (0.6 g) in 20 mL of DMF, and en (10 mL) was added to the solution of nickel nitrate with stirring at ambient temperature; this solution was labeled as solution-IV. Solution-III (38 g) was mixed with solution-IV to give the mother liquor for both growth of seeds and fabrication of a film of Ni(en)3Ag2I4. Functionalized Quartz Glass Surface via a Self-Assembly Monolayer (SAM). The quartz glass was cleaned using ultrasonic washing in absolute ethanol for 30 min and then immersed in an ethanol solution (50 mL) with one droplet of MPTS for 30 min. The quartz glass was taken out and cleaned using ethanol for the next growth of crystalline Ni(en)3Ag2I4 thin film. Growth of a Crystalline Film of Ni(en)3Ag2I4. The growth strategy of an integrated and homogeneous Ni(en)3Ag2I4 thin film concerns two sequential steps, as schematically illustrated in Scheme 1:

Scheme 1. Illustration of the Ni(en)3Ag2I4 Crystalline Hybrid Film Growth Strategya

a

Light blue represents the SAM-functionalized quartz glass, and light purple and purple correspond to the seeding layer and film of Ni(en)3Ag2I4. (1) The Ni(en)3Ag2I4 seeding layer was spin-coated on the SAMfunctionalized quartz glass, and the terminal −SH groups of the MPTS molecules are bound to the Ag+ ions on the surface of Ni(en)3Ag2I4 seeding crystals to affix them on the surface of the glass substrate. (2) The SAM-functionalized quartz glass with the Ni(en)3Ag2I4 seeding layer was vertically immersed in the mother liquor in a 50 mL beaker,

Figure 1. (a) Asymmetric unit with atom labeling. (b) Packing diagram viewed along the a-axis direction. (c) Anionic framework where Ag1I4 and Ag2I4 coordination tetrahedra are represented using blue and cyan, respectively. (d) Intermolecular interactions between the anionic framework and [Ni(en)3]2+ ions for hybrid Ni(en)3Ag2I4. B

DOI: 10.1021/acs.inorgchem.5b02439 Inorg. Chem. XXXX, XXX, XXX−XXX

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Figure 2. (a) TG plot and (b) PXRD profiles of Ni(en)3Ag2I4 at selected temperatures. been incorporated into our calculations. The k-point sampling in the Brillouin zone was set at 4 × 4 × 3 according to the Monkhorst−Pack scheme.29 For all relevant calculations, the plane-wave basis set cutoff was fixed at 240 eV and the convergence criterion at 1.0 × 10−5 eV· atom−1. The other calculation parameters were set at the default values in the CASTEP code.

strategy; such a method has been commonly used for the preparation of coordination polymer films.31−33 The preparation of a suitable submicron-sized seed is the critical step for fabrication of the integrated and homogeneous hybrid film; otherwise, it is impossible to get an integrated and homogeneous hybrid film (Figure S4). In order to get suitable seeding crystals, special treatments were required: the mother liquor was successively heated to 80 °C, maintained at this temperature for 72 h, heated to 100 °C for 24 h, and then gradually cooled to 35 °C with a programmed cooling process at a rate of 5 °C·min−1. The crystals were taken out and mixed with propanol, glycol, and glycerol with corresponding volume fractions of 79.3%, 15.9%, and 4.8%, where the amount of Ni(en)3Ag2I4 seeds is 0.165 mol·L−1. The mixture was milled utilizing high-energy ball milling (PM-100, Retsch India) to disperse Ni(en)3Ag2I4 seeds for 2 h at 400 rpm and then spincoated on the SAM-functionalized quartz glass. The quartz substrate with seeds was vertically immersed in the mother liquor at 35 °C for a period of time, which influences the thickness of the hybrid film, and then immersed in deionized water and methanol in sequence to remove the solvents (propanol, glycol, and glycerol), and the ions adsorbed on the surface of the hybrid film. A high-quality hybrid film was eventually obtained after dried in a heating chamber at 80 °C (see Figure 3a,b). As the growth time was increased, there was growth in the thickness of the film and inverse deterioration in transmission (Figure 3c). NIR Absorption of Ni(en)3Ag2I4. The UV−vis−NIR absorption spectra are respectively presented in Figure 4a for a polycrystalline sample of Ni(en)3Ag2I4, together with the

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RESULTS AND DISCUSSION Crystal Structure and Thermal Stability. The crystal structure of Ni(en)3Ag2I4 was previously reported in the literature.24 Herein, we describe it simply for the sake of convenient discussion in the next section. Ni(en)3Ag2I4 crystallizes in the acentrosymmetric space group P63. As displayed in Figure 1a, an asymmetric unit of Ni(en)3Ag2I4 is comprised of two Ag+, two I−, and one Ni2+ ions, together with one en molecule. The Ni1 ion occupies the Wyckoff position 2a, and its coordination octahedron, with the symmetry of a C3 point group, is built from six N atoms from three en molecules. Ag1, Ag2, and I2 are located at the Wyckoff position 2b, both Ag1 and Ag2 are coordinated by three I1 and one I2 ions to form the tetrahedral coordination sphere, and both I1 and I2 ions act as the μ2-bridged ligands. Two types of coordination tetrahedra, Ag1I4 and Ag2I4, have the symmetry with a C3 point group, and the 3-fold rotational axis passes through I2 and Ag1/Ag2 ions, where there are two types of Ag−I distances, namely, the shorter distance dAg1−I1 = dAg2−I1 = 2.8512(4) Å and the longer distance dAg2−I2 = 2.8803(12) Å. As shown in Figure 1b,c, the neighboring Ag1I4 and Ag2I4 coordination tetrahedra connect into a diamondlike (Ag2I42−)∞ inorganic framework by sharing of the vertex and the Ni(en)32+ coordination octahedra fall in the pores. Only weak van der Waals interactions are found between the (Ag2I42−)∞ inorganic framework and Ni(en)32+ coordination octahedral guests; for instance, the shorter interatomic contacts between the H atoms in en and iodides in the anionic framework, dH1A···I1#1 = 3.034 Å, dH2A···I1#2 = 3.044 Å, dH1B···I2#3 = 3.141 Å, and dH2B···I2#4 = 3.134 Å (symmetric codes: #1, 2 − x, 2 − y, 0.5 + z; #2, 2 − y, 1 + x − y, z; #3, 1 + x, 1 + y, z; #4, x, 1 + y, z), as displayed in Figure 1d, are slightly longer than the sum of the I- and H-atom van der Waals radii (3.0 Å).30 The hybrid crystals are thermally stable below 200 °C; this was confirmed by TG measurement (Figure 2a), where the weight loss corresponds to decomposition of the hybrid, and variable-temperature PXRD measurements as well. As shown in Figure 2b, the PXRD profiles are almost the same at selected temperatures below 200 °C, while the new diffractions appear when the temperature is up to 200 °C. Growth of Ni(en)3Ag2I4 on a SAM-Functionalized Quartz Glass Surface. The homogeneous and compact film of Ni(en)3Ag2I4 was fabricated using a secondary seed growth

Figure 3. (a) FESEM image of a Ni(en)3Ag2I4 hybrid film grown on the modified quartz glass by MPTS with 1 h of growth time. (b) Cross section of the FESEM image. (c) Photographs of quart glass (left) and Ni(en)3Ag2I4 hybrid films with different reaction times from 0 h (left) and 0.5 to 3 h (right), respectively. C

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Figure 4. (a) UV−vis−NIR absorption spectra of Ni(en)3Ag2I4 and Zn(en)3Ag2I4 powders. (b) Ni(en)3Ag2I4 hybrid film with growth time = 1 h and a SAM-functionalized quartz glass support with a seeding layer.

Figure 5. Plots of the conductivity against temperature in the forms of (a) σ−T (b) ln(σ)−1000/T (solid squares, experimental data; red line, fit using the Arrhenius equation and data in the temperature range of 328−433 K) for Ni(en)3Ag2I4..

isostructural Zn(en)3Ag2I4, and in Figure 4b for the film of Ni(en)3Ag2I4 (with growth time = 1 h) and the SAMfunctionalized quartz glass support with a seeding layer. Both the polycrystalline and film samples show a broad and intense absorption band centered around 870 nm. By a comparison of the isostructural hybrid compound Zn(en)3Ag2I4 (Figure 4a), it can be found that the absorption bands of both Ni(en)3Ag2I4 and Zn(en)3Ag2I4 are almost the same in the UV region (λ < 400 nm) and NIR regime (λ > 1200 nm), while they are quite different in the spectroscopy region between 400 and 1200 nm. It is worth noting that both Ni(en)3Ag2I4 and Zn(en)3Ag2I4 show rather analogous crystal structures with the same space group (P63), similar lattice parameters, and almost the same packing structure as well (Table S1 and Figure S1);24 however, the cations Ni(en)32+ in Ni(en)3Ag2I4 and Zn(en)32+ in Zn(en)3Ag2I4 have distinct electronic structure because Ni2+ and Zn2+ possess open-shell (d8) and closed-shell (d10) electronic configurations, respectively. The absorption bands in the UV region are assigned to the electronic transitions within the diamondlike (Ag2I4)∞ inorganic framework for both Ni(en)3Ag2I4 and Zn(en)3Ag2I4, and the NIR absorption band centered at 870 nm in Ni(en)3Ag2I4 is contributed to d−d transition of a Ni2+ ion. Such a NIR d−d transition band was also observed in other Ni(en)32+ hybrid compounds with λmax ≈ 843 nm but was much weaker with respect to the shortwavelength absorption bands,34 indicating that the anionic matrix in hybrid compounds significantly affects the d−d transition nature of the Ni(en)32+ countercation. Theoretically, in a centrosymmetric complex, such as an octahedral complex, the d−d transitions are forbidden by the Laporte rule;35 however, such forbidden transitions are allowed if the center of symmetry is disrupted, and disruption of the center of symmetry occurs for various reasons, such as the Jahn−Teller effect and the vibronic coupling, in which a molecular vibration

occurs together with a d−d transition. In addition, it is possible to mix d and p orbitals when there is no center of symmetry, in such a case, the d-d transitions are also allowed. As described in the crystal structure of Ni(en)3Ag2I4, the Ni(en)32+ cation, which possesses C3 point-group symmetry, has no center of symmetry, and it is understandable to observe an intense d−d transition band in Ni(en)3Ag2I4. The band centered at 544 nm is assigned to the change-transfer transition from the diamondlike (Ag2I4)∞ inorganic framework to the Ni(en)32+ cation in Ni(en)3Ag2I4, and this assignment is further confirmed by electronic band structure analysis. It is mentioned that the SAM-functionalized quartz glass with the Ni(en)3Ag2I4 seeding layer shows weak absorbance in the whole spectroscopy regime in Figure 4b regarding the Ni(en)3Ag2I4 film owing to quite a smaller amount of Ni(en)3Ag2I4 on the surface of quartz glass. Conductivity of Ni(en)3Ag2I4. The dc conductivity (σ) against temperature was plotted in the forms of σ−T and ln(σ)−1000/T for the powdered pellet sample of Ni(en)3Ag2I4. As shown in Figure 5a, when the temperature is elevated, σ of the Ni(en)3Ag2I4 pellet increases from 3.14 × 10−6 S·cm−1 at 293 K to 1.35 × 10−4 S·cm−1 at 433 K, exhibiting thermally activated semiconducting behavior. However, as displayed in Figure 5b, the plot of ln(σ) vs 1000/T is not linear in the whole range of temperature of 293−433 K. The Ea value was estimated to be 0.46 eV using Arrhenius equation (1) and the conductivity in the temperature range of 328−433 K, where there exists a linear relationship between ln(σ) and 1/T for Ni(en)3Ag2I4. ln σ = ln σ0 − D

Ea kBT

(1) DOI: 10.1021/acs.inorgchem.5b02439 Inorg. Chem. XXXX, XXX, XXX−XXX

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Figure 6. (a) Several highest occupied and lowest unoccupied bands in Ni(en)3Ag2I4, where the Fermi levels are shown by dashed lines. (b and c) Magnified views of the highest occupied and several lowest unoccupied bands and k points: G = (0, 0, 0), A = (0, 0, 0.5), H = (−0.333, 0.667, 0.5), K = (−0.333, 0.667, 0), M = (0, 0.5, 0), and L = (0, 0.5, 0.5). (d) DOS, where Fermi levels are shown by dashed lines.

In eq 1, the symbol σ represents the dc conductivity at temperature T (K), σ0 is the preexponential factor, Ea is the activation energy barrier of the semiconductor, and kB is the Boltzmann constant. Electronic Band Structure of Ni(en) 3Ag 2 I4 . The electronic band structure was analyzed for Ni(en)3Ag2I4, and the calculated bands are shown in Figure 6a along the highsymmetry directions of the Brillouin zone. The magnified views of the highest occupied band and several lowest unoccupied bands are displayed in parts b and c of Figure 6, respectively. The band structure features a multiband structure with intermediate band sets located in the energy range of 0.03− 0.13 eV in the lowest unoccupied band and between −3.0 and −1.6 eV in the highest occupied band. The total density of states (DOSs) and partial DOSs arising from the anionic (Ag2I42−)∞ framework are illustrated in Figure 6d, which shows that the highest occupied and lowest unoccupied band orbitals are comprised of the molecular orbitals of Ni(en)32+ cations and that the next-highest occupied and next-lowest unoccupied band orbitals are comprised of the atomic orbitals of Ag+ and I− ions. This means that NIR absorption arises from the electron transition within Ni(en)32+ cations and the band centered at 544 nm originating from charge-transfer transition between the anionic (Ag2I42−)∞ framework and the Ni(en)32+ cations. It is noted that (1) the calculated band gap is 1.762 eV, corresponding to an electron transition wavelength of ca. 704 nm, which is obviously less than the wavelength value of the NIR absorption band maximum, and this difference is attributed to the limitations of DFT methods.36−38 (2) All of the highest occupied and lowest unoccupied bands are flat along the high-symmetry directions of the Brillouin zone, indicating that there is weak orbital interaction between the neighboring Ni(en)32+ cations; this is in well agreement with the crystal structure analysis because the neighboring cations

occupied in the pores of anionic (Ag2I42−)∞ framework are far from each other, with the shortest distance between the neighboring cations dNi···Ni > 7.2 Å along the c-axis direction. (3) The energy gap is 1.989 eV between the next-highest occupied and next-lowest unoccupied bands, indicating that the anionic (Ag2I42−)∞ framework shows narrow-band semiconductor character.

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CONCLUSION In summary, the organic−inorganic hybrid crystal Ni(en)3Ag2I4 shows a diamondlike inorganic framework, which is comprised of vertex-shared AgI4 tetrahedra and features the electronic structure character of a narrow-band semiconductor. The Ni(en)32+ cations are occupied in the cavities of the diamondlike inorganic framework and give a broad and intense NIR absorbance centered at 870 nm, which arises from the d−d electronic transition of Ni2+ ions. The integrated, dense, and transparent crystalline film was fabricated for Ni(en)3Ag2I4 through the secondary seed growth approach, and the thickness of the film is tunable via control of the growth time. Such types of crystalline films have promising applications in NIR shielding and other devices.

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ASSOCIATED CONTENT

S Supporting Information *

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.inorgchem.5b02439. Lattice parameters of both Ni(en)3Ag2I4 and Zn(en)3Ag2I4 in Table S1, crystal structure diagrams and energy band with DOS of Zn(en)3Ag2I4, seeding-layer SEM image and cross section of Ni(en)3Ag2I4 on the surface of quartz glass, photograph of Ni(en)3Ag2I4 on E

DOI: 10.1021/acs.inorgchem.5b02439 Inorg. Chem. XXXX, XXX, XXX−XXX

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the surface of quartz glass, SEM image and cross section of Ni(en)3Ag2I4 on the surface of a gold electrode and a nonwoven fabrics substrate (PDF)

AUTHOR INFORMATION

Corresponding Authors

*E-mail: [email protected]. Tel.: +86 25 58139476. Fax: +86 25 58139481. *E-mail: [email protected]. Tel.: +86 25 58139476. Fax: +86 25 58139481. Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS The authors thank the Priority Academic Program Development of Jiangsu Higher Education Institutions, the National Nature Science Foundation of China (Grants 21271103 and 21176115), and the Innovative Research Team Program by the Ministry of Education of China (Grant IRT13070) for financial support.

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DOI: 10.1021/acs.inorgchem.5b02439 Inorg. Chem. XXXX, XXX, XXX−XXX