Nanoparticles embedded into glass matrices: glass nanocomposites

doi:10.1007/s11706-022-0607-7

Front. Mater. Sci.

2022, Vol. 16

Issue (3) : 220607 https://doi.org/10.1007/s11706-022-0607-7

REVIEW ARTICLE

Nanoparticles embedded into glass matrices: glass nanocomposites

Javier FONSECA(

)

Department of Chemical Engineering, Northeastern University, Boston 02115, USA

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Abstract

Research on glass nanocomposites (GNCs) has been very active in the past decades. GNCs have attracted — and still do — great interest in the fields of optoelectronics, photonics, sensing, electrochemistry, catalysis, biomedicine, and art. In this review, the potential applications of GNCs in these fields are briefly described to show the reader the possibilities of these materials. The most important synthesis methods of GNCs (melt-quenching, sol-gel, ion implantation, ion-exchange, staining process, spark plasma sintering, radio frequency sputtering, spray pyrolysis, and chemical vapor deposition techniques) are extensively explained. The major aim of this review is to systematize our knowledge about the synthesis of GNCs and to explore the mechanisms of formation and growth of NPs within glass matrices. The size-controlled preparation of NPs within glass matrices, which remains a challenge, is essential for advanced applications. Therefore, a thorough understanding of GNC synthesis techniques is expected to facilitate the preparation of innovative GNCs.

Keywords glass nanocomposites melt-quenching sol-gel ion implantation ion-exchange

Corresponding Author(s): Javier FONSECA

Issue Date: 12 October 2022

Cite this article:

Javier FONSECA. Nanoparticles embedded into glass matrices: glass nanocomposites[J]. Front. Mater. Sci., 2022, 16(3): 220607.

URL:

https://academic.hep.com.cn/foms/EN/10.1007/s11706-022-0607-7
https://academic.hep.com.cn/foms/EN/Y2022/V16/I3/220607

Fig.1 Examples of all-optical devices: (a) directional coupler (self-induced switching); (b) Mach?Zehnder interferometer. The response of linear (dashed lines) and non-linear (solid lines) materials is also illustrated.

Fig.2 LSPR generated by incising light on a metal NP.

Tab.1 Comparison of the different GNC synthesis methods

Fig.3 Schematic illustration of GNC preparation using melt-quenching technique.

Composite	Host matrix	Reinforcement	Size of NPs (min?max (mean))/nm	Loading of NPs/wt.% in excess	Melt-quenching technique	Applications	Ref.
CdSe QDs@silicate glass	Silicate glass (56 wt.% SiO₂, 8 wt.% B₂O₃, 24 wt.% K₂O, 3 wt.% CaO, and 9 wt.% BaO)	CdSe QDs	(4.8)	0.5?1	Concomitant synthesis of glass matrix and NPs: melt-quenching (melting at 1400 °C for 1.5 h)	?	[164]
Cu NPs@tellurite glass	Tellurite glass (87.81 wt.% TeO₂, 7.76 wt.% Sb₂O₃, 2.33 wt.% Yb₂O₃, 0.97 wt.% Ce₂O₃, and 1.13 wt.% Er₂O₃)	Cu NPs	5?20	0.23	Concomitant synthesis of glass matrix and NPs: melt-quenching (melting at 800 °C for 3 min), Sb₂O₃ redox route	IR optical devices	[165]
Cu NPs@tellurite glass	Tellurite glass (90.94 wt.% TeO₂, 7.91 wt.% Sb₂O₃, and 1.15 wt.% Er₂O₃)	Cu NPs	(20)	0.24	Concomitant synthesis of glass matrix and NPs: melt-quenching (melting at 800 °C for 3 min), Sb₂O₃ redox route	Lasers (biomedical and bioimaging fields); thermophotovoltaic conversion of thermal radiation	[166]
Au NPs@lanthanum borate glass	Lanthanum borate glass (23.05 wt.% La₂O₃, 47.38 wt.% PbO, and 29.56 wt.% B₂O₃)	Au NPs	30?40	0.11	Concomitant synthesis of glass matrix and NPs: melt-quenching (melting at 1100 °C for 30 min); annealing (at 500 °C for 2 h)	NLO devices: β_{(532 nm)} = 2 × 10^?11 m·W^?1	[167]
Au NPs@lanthanum borate glass	Lanthanum borate glass (23.05 wt.% La₂O₃, 47.38 wt.% PbO, and 29.56 wt.% B₂O₃)	Au NPs	30?40	1.10		NLO devices: β_{(532 nm)} = 1.4 × 10^?12 m·W^?1	[167]
Au NPs@lanthanum borate glass	Lanthanum borate glass (23.05 wt.% La₂O₃, 47.38 wt.% PbO, and 29.56 wt.% B₂O₃)	Au NPs	(40)	0.001	Concomitant synthesis of glass matrix and NPs: melt-quenching (melting at 1100 °C for 30 min); annealing (at 500 °C for 2 h)	NLO devices: n_{2(532 nm)} = 6.7 × 10^?14 m²·W^?1	[168]
Au NPs@lanthanum borate glass	Lanthanum borate glass (23.05 wt.% La₂O₃, 47.38 wt.% PbO, and 29.56 wt.% B₂O₃)	Au NPs	(40)	0.001		NLO devices: n_{2(532 nm)} = 5.6 × 10^?14 m²·W^?1	[168]
Au NPs@bismuthate glass	Bismuthate glass (91.22 wt.% Bi₂O₃, 6.82 wt.% B₂O₃, and 1.96 wt.% SiO₂)	Au NPs	3?9	?	Concomitant synthesis of glass matrix and NPs: melt-quenching (melting at 1200 °C for 30 min); annealing (at 390 °C for 2 h)	NLO devices: χ⁽³⁾_{(800 nm)} = 4.88 × 10^?10 esu	[169]
Ag NPs@oxyfluoride glass	Oxyfluoride glass (36.10 wt.% SiO₂, 19.61 wt.% Al₂O₃, 14.91 wt.% ZnF₂, 21.14 wt.% SrF₂, 5.70 wt.% B₂O₃, and 2.54 wt.% Na₂O)	Ag NPs	(< 5)	5.23	Concomitant synthesis of glass matrix and NPs: melt-quenching (melting at 1450 °C for 45 min)	LED illumination and solar cells	[170]
Ag NPs@oxyfluoride glass	Oxyfluoride glass (35.06 wt.% SiO₂, 19.04 wt.% Al₂O₃, 14.48 wt.% ZnF₂, 20.53 wt.% SrF₂, 5.54 wt.% B₂O₃, 2.47 wt.% Na₂O, and 2.89 wt.% YbF₃)	Ag NPs	(< 5)	5.14		LED illumination and solar cells	[170]
Ag NPs@tellurite glass	Tellurite glass (85.70 wt.% TeO₂, 11.58 wt.% ZnO, and 2.72 wt.% Er₂O₃)	Ag NPs	(12)	0.38	Concomitant synthesis of glass matrix and NPs: melt-quenching (melting at 800 °C for 15 min); annealing (At 350 °C for 8 h)	Nanophotonics	[97]
Ag NPs@sodium borosilicate glass	Sodium borosilicate glass (62.48 wt.% SiO₂, 8.78 wt.% B₂O₃, 11.72 wt.% Na₂O, 3.97 wt.% NaF, and 13.06 wt.% SrO)	Ag NPs	(3.5)	2.49	Concomitant synthesis of glass matrix and NPs: melt-quenching (melting at 1450 °C for 1 h); annealing (at 450 °C for 2 h)	Solid-state lasers	[171]
Ag NPs@SmF₃-doped sodium borosilicate glass	Sodium borosilicate glass (62.48 wt.% SiO₂, 8.78 wt.% B₂O₃, 11.72 wt.% Na₂O, 3.97 wt.% NaF, 13.06 wt.% SrO, and 2.49 wt.% SmF₃)	Ag NPs	(7.5)	2.49		Solid-state lasers	[171]
Bi-coated Ag NPs@bismuthate glass	Bismuthate glass (79.13 wt.% Bi₂O₃, 12 wt.% K₂O, and 8.87 wt.% B₂O₃)	Ag NPs coated with Bi	5?15	0.007	Concomitant synthesis of glass matrix and NPs: melt-quenching (melting at 1100 °C for 10 min); annealing (at 350 °C for 2 h)	Nanophotonics and optoelectronics	[172]
Bi-coated Ag NPs@bismuthate glass	Bismuthate glass (79.13 wt.% Bi₂O₃, 12 wt.% K₂O, and 8.87 wt.% B₂O₃)	Ag NPs coated with Bi	10?35	0.03		Nanophotonics and optoelectronics	[172]
Ag NPs@calcium fluorophosphate glass	Calcium fluorophosphate glass (12.63 wt.% CaO, 4.40 wt.% CaF₂, 79.94 wt.% P₂O₅, and 3.03 wt.% SnO)	Ag NPs	(5)	2.37	Heat-assisted precipitation of NPs: melt-quenching for glass preparation (melting at 1200 °C for 15 min); heat-assisted NP precipitation (at 550 °C for 10 h)	?	[173]
Ag NPs@calcium fluorophosphate glass	Calcium fluorophosphate glass (12.63 wt.% CaO, 4.40 wt.% CaF₂, 79.94 wt.% P₂O₅, and 3.03 wt.% SnO)	Ag NPs	(15)	2.37	Heat-assisted precipitation of NPs: melt-quenching for glass preparation (melting at 1200 °C for 15 min); heat-assisted NP precipitation (at 550 °C for 30 h)
Ag NPs@calcium fluorophosphate glass	Calcium fluorophosphate glass (12.63 wt.% CaO, 4.40 wt.% CaF₂, 79.94 wt.% P₂O₅, and 3.03 wt.% SnO)	Ag NPs	(42)	2.37	Heat-assisted precipitation of NPs: melt-quenching for glass preparation (melting at 1200 °C for 15 min); heat-assisted NP precipitation (at 550 °C for 50 h)
Ag NPs@lanthanum sodium borate glass	Lanthanum sodium borate glass (67.23 wt.% B₂O₃, 11.14 wt.% Na₂O, 19.52 wt.% La₂O₃, and 2.11 wt.% Eu₂O₃)	Ag NPs	(2.72)	0.17	Heat-assisted precipitation of NPs: melt-quenching for glass preparation (melting at 1050 °C for 2 h); heat-assisted NP precipitation (at 450 °C for 10 h)	Solid-state lasers	[174]
Ag NPs@lanthanum sodium borate glass	Lanthanum sodium borate glass (67.23 wt.% B₂O₃, 11.14 wt.% Na₂O, 19.52 wt.% La₂O₃, and 2.11 wt.% Eu₂O₃)	Ag NPs	(4.64)	0.17	Heat-assisted precipitation of NPs: melt-quenching for glass preparation (melting at 1050 °C for 2 h); heat-assisted NP precipitation (at 450 °C for 15 h)
Ag NPs@lanthanum sodium borate glass	Lanthanum sodium borate glass (67.23 wt.% B₂O₃, 11.14 wt.% Na₂O, 19.52 wt.% La₂O₃, and 2.11 wt.% Eu₂O₃)	Ag NPs	(6.40)	0.17	Heat-assisted precipitation of NPs: melt-quenching for glass preparation (melting at 1050 °C for 2 h); heat-assisted NP precipitation (at 450 °C for 20 h)
Ag NPs/Au NPs@phosphate glass	Phosphate glass (82.58 wt.% P₂O₅, 3.69 wt.% MgO, 11.10 wt.% ZnSO₄, and 2.63 wt.% Eu₂O₃)	Ag NPs and Au NPs	(27.65)	0.44 wt.% Ag, 1.5 wt.% Au	Heat-assisted precipitation of NPs: melt-quenching for glass preparation (melting at 1100 °C for 1.5 h); heat-assisted NP precipitation (at 300 °C for 3 h)	Solid-state lasers	[175]
Ag NPs@silicate glass	Silicate glass (70.02 wt.% SiO₂, 9.34 wt.% CaO, and 20.64 wt.% Na₂O)	Ag NPs	1?8	?	Irradiation-assisted precipitation of NPs: melt-quenching for glass preparation (melting at 1550 °C for 1 h); femtosecond laser irradiation; annealing (at 550 °C for 10 min)	Art, optical memory, and all-optical switching devices	[176]
Au NPs@silicate glass	Silicate glass (70.02 wt.% SiO₂, 9.34 wt.% CaO, and 20.64 wt.% Na₂O)	Au NPs	6?8	?	Irradiation-assisted precipitation of NPs: melt-quenching for glass preparation (melting at 1550 °C for 1 h); femtosecond laser irradiation; annealing (at 550 °C for 30 min)	Art, optical memory, and all-optical switching devices	[177]
Ag NPs/Au NPs@silicate glass	Silicate glass (70.02 wt.% SiO₂, 9.34 wt.% CaO, and 20.64 wt.% Na₂O)	Ag NPs and Au NPs	?	?	Irradiation-assisted precipitation of NPs: melt-quenching for glass preparation (melting at 1550 °C for 1 h); femtosecond laser irradiation; annealing	Art, optical memory, and all-optical switching devices	[178]
Cu NPs@borate glass	Borate glass (6.78 wt.% K₂O, 4.04 wt.% CaO, and 89.19 wt.% B₂O₃)	Cu NPs	3?5 (4)	?	Irradiation-assisted precipitation of NPs: melt-quenching for glass preparation (melting at 1000 °C for 30 min); annealing (at 300 °C for 2 h); femtosecond laser irradiation	Art, optical memory, and all-optical switching devices	[179]
Cu NPs@soda-lime silicate glass	Soda-lime silicate glass (46.62 wt.% SiO₂, 18.37 wt.% B₂O₃, 7.19 wt.% MgO, 9.62 wt.% Na₂O, and 18.20 wt.% Al₂O₃)	Cu NPs	(9)	?	Irradiation-assisted precipitation of NPs: melt-quenching for glass preparation (melting at 1400 °C for 1 h); annealing (at 400 °C for 12 h); femtosecond laser irradiation; heat treatment (at 600 °C for 1 h)	Art, optical memory, and all-optical switching devices	[180]
Ag NPs@borosilicate glass	Borosilicate glass (75.22 wt.% SiO₂, 16.98 wt.% Na₂O, 3.01 wt.% Al₂O₃, and 4.79 wt.% CaO)	Ag NPs	1?5.6 (2.8)	?	Irradiation-assisted precipitation of NPs: melt-quenching for glass preparation (melting at 1450 °C for 4 h); X-ray irradiation (34 min); heat treatment (at 400 °C for 15 min)	Art, optical memory, and all-optical switching devices	[181]
Au NPs@borosilicate glass	Borosilicate glass (72.68 wt.% SiO₂, 15.67 wt.% Na₂O, 2.19 wt.% Al₂O₃, and 9.45 wt.% CaO)	Au NPs	(1.8)	?	Irradiation-assisted precipitation of NPs: melt-quenching for glass preparation (melting at 1400 °C for 3 h); annealing (at 550 °C for 15 min); X-ray irradiation (5 min); heat treatment (at 600 °C for 20 min or for 3 h)	Art, optical memory, and all-optical switching devices	[182]
Cu NPs@silicate glass	Silicate glass (75.32 wt.% SiO₂, 16.8 wt.% Na₂O, 7.6 wt.% CaO, and 0.28 wt.% SnO₂)	Cu NPs	2?8	?	Irradiation-assisted precipitation of NPs: melt-quenching for glass preparation; ion irradiation; heat treatment (at 400 °C for 10 h)	?	[183]
Ag NPs@phosphate glass	Phosphate glass (77.46 wt.% P₂O₅, 3.79 wt.% MgO, 15.19 wt.% ZnSO₄, and 3.56 wt.% Ho₂O₃)	Ag NPs	(4.93)	0.4	NPs added before glass formation: melt-quenching for glass preparation (melting at 1100 °C for 1.5 h); annealing (at 300 °C for 3.5 h)	Solid-state lasers	[75]
NiO NPs@borate glass	Borate glass (58.10 wt.% B₂O₃, 31.12 wt.% ZnO, and 10.78 wt.% Na₂O)	NiO NPs	(70)^a)	0.52	NPs added before glass formation: melt-quenching for glass preparation (melting at 1200 °C for 2 h); annealing (at 400 °C for 1 h)	Semiconductor applications	[184]
Sm₂O₃ NPs@bio-borosilicate glass	Bio-borosilicate glass (10.17 wt.% SiO₂, 14.15 wt.% B₂O₃, and 75.68 wt.% TeO₂)	Sm₂O₃ NPs	(71.74)	8.37	NPs added before glass formation: melt-quenching for glass preparation (melting at 1050 °C for 3 h); annealing (at 400 °C for 2 h)	Non-linear optics	[185]
CdFe₂O₄/SiO₂ NPs@antimony phosphate glass	Antimony phosphate glass (68.47 wt.% SbPO₄, 16.47 wt.% ZnO, and 15.06 wt.% PbO)	CdFe₂O₄/SiO₂ NPs	(3.5)	2.5	NPs added to a molten glass: melt-quenching for glass preparation (melting at 1100 °C for 30 min); NPs added to a molten glass; melt-quenching for embedding CdFe₂O₄/SiO₂ NPs (melting at 1100 °C for 7 min)	Magneto-optical devices	[186]
Fe₃O₄ NPs@tellurite glass	Tellurite glass (88.44 wt.% TeO₂, and 11.56 wt.% ZnO)	Fe₃O₄ NPs	18?70^(a)	3.18	NPs added before glass formation: melt-quenching for glass preparation (melting at 850 °C for 20 min); annealing (at 300 °C for 3 h)	Magneto-optical devices	[187]
Fe₃O₄ NPs@tellurite glass	Tellurite glass (86.97 wt.% TeO₂, 10.17 wt.% ZnO, 0.21 wt.% LiO, and 2.66 wt.% Er₂O₃)	Fe₃O₄ NPs	18?70^(a)	2.35	NPs added before glass formation: melt-quenching for glass preparation (melting at 850 °C for 20 min); annealing (at 300 °C for 3 h)	Magneto-optical devices	[188]
Fe₃O₄ NPs@phosphate glass	Phosphate glass (77.24 wt.% P₂O₅, 19.68 wt.% ZnO, and 3.08 wt.% Er₂O₃)	Fe₃O₄ NPs	(31)	2.72	NPs added before glass formation: melt-quenching for glass preparation (melting at 950 °C for 1 h); annealing (at 300 °C for 3 h)	Magneto-optical devices	[189]
Fe₃O₄ NPs@phosphate glass	Phosphate glass (77.10 wt.% P₂O₅, 19.79 wt.% ZnO, and 3.10 wt.% Er₂O₃)	Fe₃O₄ NPs	(26)	3.6222		Magneto-optical devices	[189]

Tab.2 GNCs prepared by melt-quenching techniques [75,97,164–189]

Fig.5 (a) UV-vis spectra of GNCs. Notation: A05H8 = Composite made from Ag NPs (0.5 mol.% AgCl precursor) embedded into an Er³⁺-doped tellurite glass; A10H8 = Composite made from Ag NPs (1 mol.% AgCl precursor) embedded into an Er³⁺-doped tellurite glass. E1A05H8 revealed three prominent plasmon peaks at 562, 598, and 628 nm. E0A10H8 showed two peaks at 550 and 578 nm. This difference between E1A05H8 and E0A10H8 was attributed to the non-spherical Ag NPs. (b) Size distribution of Ag NPs (0.5 mol.% AgCl precursor) embedded into an Er³⁺-doped tellurite glass. (c) TEM image of Ag NPs (0.5 mol.% AgCl precursor) embedded into an Er³⁺-doped tellurite glass. (d) HRTEM micrograph of Ag NPs (0.5 mol.% AgCl precursor) embedded into an Er³⁺-doped tellurite glass. The image shows a 0.125 nm fringe spacing corresponding to the (3 1 1) Ag lattice spacing. Reproduced with permission from Ref. [97] (Copyright 2013 Elsevier).

Fig.6 (a) TEM image of Ag NPs embedded in calcium fluorophosphate glass (heated at 550 °C for 10 h). Inset: the size distribution of Ag NPs. (b) HRTEM of Ag NPs@calcium fluorophosphate glass (heated at 550 °C for 10 h). (c) TEM image of Ag NPs embedded in calcium fluorophosphate glass (heated at 550 °C for 30 h). Inset: the size distribution of Ag NPs. (d) Selected area electron diffraction (SAED) image of Ag NPs embedded in calcium fluorophosphate glass (heated at 550 °C for 30 h). Reproduced with permission from Ref. [173] (Copyright 2015 Elsevier).

Fig.7 (a) TEM image of CsPbBr₃ QDs@sodium borosilicate glass. (b) TEM image of CsPbBr₃ QDs/Ag NPs@sodium borosilicate glass (0.1 mol.% of Ag₂O precursor). Notation: red spheres denote the CsPbBr₃ QDs. Reproduced with permission from Ref. [202] (Copyright 2019 John Wiley & Sons).

Fig.8 CsPbBr₃ QDs/Ag NPs@sodium borosilicate glass (0.1 mol.% of Ag₂O precursor) in water under the irradiation of a 400 nm lamp. Reproduced with permission from Ref. [202] (Copyright 2019 John Wiley & Sons).

Fig.9 (a) Photograph of the composite after femtosecond laser irradiation and annealing at 400 °C for 30 min. (b) Photograph of the composite after femtosecond laser irradiation and annealing at 570 °C for 30 min. The average laser power was 10 mW. Reproduced with permission from Ref. [178] (Copyright 2006 Elsevier).

Fig.11 (a) Photograph of the glass sample with a grating pattern after irradiation with a femtosecond laser. (b) Optical microscope photograph of the enlarged grating pattern. (c)(d) Photographs of the diffraction patterns of glass samples before irradiation (panel (c); no diffraction pattern was observed in glass) and after irradiation (panel (d); a diffraction pattern was observed when the grating pattern was irradiated by a 532 nm laser) with a femtosecond laser. Reproduced with permission from Ref. [179] (Copyright 2010 Elsevier).

Fig.12 Schematic illustration of (a) the synthesis of Fe_3?δO₄@SiO₂ NPs and (b) the preparation of the phosphate glasses containing monodisperse Fe_3?δO₄@SiO₂ NPs. Reproduced with permission from Ref. [214] (Copyright 2020 Elsevier).

Fig.13 M?H curves at room temperature for (a) Fe₃O₄ NPs and (b) GNCs (Fe₃O₄ NPs@phosphate glasses) with different concentrations of embedded Fe₃O₄ NPs. Reproduced with permission from Ref. [189] (Copyright 2015 Elsevier).

Fig.14 Schematic illustration of the sol-gel process sequence to prepare NPs embedded into glass matrices.

Composite	Host matrix	Reinforcement	Size of NPs (min?max (mean))/nm	Loading of NPs/wt.%	Sol-gel technique	Application	Ref.
Ag NPs@silica glass (Ag·4SiO₂)	Silica glass	Ag NPs	9.0?30.9 (19.5)	28.7	Concomitant synthesis of glass matrix and NPs: tethering metal precursors to the matrix during sol-gel processing	?	[241]
Ag NPs@silica glass (Ag·12SiO₂)	Silica glass	Ag NPs	?	10.22
Co NPs@silica glass (Co·SiO₂)	Silica glass	Co NPs	11.0?24.9 (17.4)	47.51
Cu NPs@silica glass (Cu·SiO₂)	Silica glass	Cu NPs	1.5?7.4 (3.9)	46.17
Ni NPs@silica glass (Ni·SiO₂)^a)	Silica glass	Ni NPs	37.5?62.4 (50.3)	43.7
Ni NPs@silica glass (Ni·2SiO₂)^a)	Silica glass	Ni NPs	Bimodal particle distribution: 7.5?12.4, 27.5?72.4	31.08
Ni NPs@silica glass (Ni·3SiO₂)^a)	Silica glass	Ni NPs	Bimodal particle distribution: 2.5?22.4, 62.5?102.4	20.05
Ni NPs@silica glass (Ni·5.5SiO₂)^a)	Silica glass	Ni NPs	Bimodal particle distribution: 2.5?12.4, 32.5?57.4	14.01
Ni NPs@silica glass (Ni·10SiO₂)^a)	Silica glass	Ni NPs	12.5?47.4 (22.9)	6.99
Ni NPs@silica glass (Ni·33SiO₂)^a)	Silica glass	Ni NPs	2.5?12.4 (5.9)	2.65
Pd NPs@silica glass (Pd·2SiO₂)	Silica glass	Pd NPs	1.8?4.2 (3.0)	44.81
Pd NPs@silica glass (Pd·4.5SiO₂)	Silica glass	Pd NPs	?	26.03
Pd NPs@silica glass (Pd·7SiO₂)	Silica glass	Pd NPs	1.8?4.2 (2.8)	18.12
Pd NPs@silica glass (Pd·12SiO₂)	Silica glass	Pd NPs	?	10.84
Pd NPs@silica glass (Pd·22SiO₂)	Silica glass	Pd NPs	?	7.18
Pd NPs@silica glass (Pd·32SiO₂)	Silica glass	Pd NPs	1.3?3.7 (2.4)	5.52
Pd NPs@silica glass (Pd·15SiO₂)	Silica glass	Pd NPs	2.8?5.2 (3.8)	9.36
Pt NPs@silica glass (Pt·32SiO₂)	Silica glass	Pt NPs	0.8?4.2 (2.5)	7.93
Pt NPs@silica glass^a)	Silica glass	Pt NPs	(7.1)	17	Concomitant synthesis of glass matrix and NPs: tethering metal precursors to the matrix during sol-gel processing	?	[242]
Pt NPs@silica glass^b)	Silica glass	Pt NPs	(3.5)	24.8
Pt NPs@silica glass^c)	Silica glass	Pt NPs	(4.0)	24.3
Pt NPs@silica glass^d)	Silica glass	Pt NPs	(5.0)	21.5
Ni NPs@silica glass^b)e)	Silica glass	Ni NPs	(8.5)	4	Concomitant synthesis of glass matrix and NPs: tethering metal precursors to the matrix during sol-gel processing	?	[243]
Ni NPs@silica glass^b)f)	Silica glass	Ni NPs	(8.5)	9
Ni NPs@silica glass^b)g)	Silica glass	Ni NPs	(8.2)	24
Ni NPs@silica glass^b)h)	Silica glass	Ni NPs	(8.5)	10
Fe₂P NCs@silica xerogel	Silica xerogel	Fe₂P NCs	(4.6)	6.64	Concomitant synthesis of glass matrix and NPs: tethering metal precursors to the matrix during sol-gel processing	?	[244]
RuP NCs@silica xerogel	Silica xerogel	RuP NCs	(4.7)	8.23
Co₂P NCs@silica xerogel	Silica xerogel	Co₂P NCs	(5.0)	4.96
Rh₂P NCs@silica xerogel	Silica xerogel	Rh₂P NCs	(2.0)	8.79
Ni₂P NCs@silica xerogel	Silica xerogel	Ni₂P NCs	(2.6)	6.83
Pd₅P₂ NCs@silica xerogel	Silica xerogel	Pd₅P₂ NCs	(11.3)	25.84
PtP₂ NCs@silica xerogel	Silica xerogel	PtP₂ NCs	(4)	2.77
Co₃C NCs@silica xerogel	Silica xerogel	Co₃C NCs	10?46 (25)	?	Concomitant synthesis of glass matrix and NPs: tethering metal precursors to the matrix during sol-gel processing	?	[245]
Ge NCs@silica xerogel	Silica xerogel	Ge NCs	2.5?14.5 (6.7)	?	Concomitant synthesis of glass matrix and NPs: tethering metal precursors to the matrix during sol-gel processing	?	[246]
Os NPs@silica xerogel	Silica xerogel	Os NPs	1?7 (2.1)	0.2?1	Concomitant synthesis of glass matrix and NPs: tethering metal precursors to the matrix during sol-gel processing	?	[247]
PtSn@silica xerogel	Silica xerogel	PtSn alloy NPs	2?14 (6)	?		?	[247]
CdS QDs@sodium borosilicate glassⁱ⁾	Sodium borosilicate glass (33.33 wt.% SiO₂, 33.33 wt.% B₂O₃, and 33.33 wt.% Na₂O)	CdS QDs	(18.4)	?	Concomitant synthesis of glass matrix and NPs	Solar concentration; lasers	[248]
CdS QDs@sodium borosilicate glass^j)	Sodium borosilicate glass (33.33 wt.% SiO₂, 33.33 wt.% B₂O₃, and 33.33 wt.% Na₂O)	CdS QDs	(15.4)	?
CdS QDs@sodium borosilicate glass^k)	Sodium borosilicate glass (33.33 wt.% SiO₂, 33.33 wt.% B₂O₃, and 33.33 wt.% Na₂O)	CdS QDs	(5.7)	?
CdS QDs@sodium borosilicate glass^l)	Sodium borosilicate glass (33.33 wt.% SiO₂, 33.33 wt.% B₂O₃, and 33.33 wt.% Na₂O)	CdS QDs	(4.3)	?
Sb NPs@sodium borosilicate glass	Sodium borosilicate glass (72.88 wt.% SiO₂, 21.38 wt.% B₂O₃, and 5.74 wt.% Na₂O)	Sb NPs	(32.63)	1.5	Concomitant synthesis of glass matrix and NPs: sol-gel method combined with heat treatment in a suitable atmosphere	NLO devices: χ⁽³⁾_{(800 nm)} = 4.85 × 10^?11 esu	[249]
Cu NPs@sodium borosilicate glass	Sodium borosilicate glass (72.88 wt.% SiO₂, 21.38 wt.% B₂O₃, and 5.74 wt.% Na₂O)	Cu NPs	1.5?5 (2.7)	1.25	Concomitant synthesis of glass matrix and NPs: sol-gel method combined with heat treatment in a suitable atmosphere	NLO devices: χ⁽³⁾_{(800 nm)} = 2.41 × 10^?11 esu	[250]
Cu₂In NPs@sodium borosilicate glass	Sodium borosilicate glass (72.88 wt.% SiO₂, 21.38 wt.% B₂O₃, and 5.74 wt.% Na₂O)	Cu₂In NPs	(30.28)	1.5	Concomitant synthesis of glass matrix and NPs: sol-gel method combined with heat treatment in a suitable atmosphere	NLO devices: χ⁽³⁾_{(800 nm)} = 3.32 × 10^?10 esu	[15]
In₂O₃ NCs@silica glass	Silica glass	In₂O₃ NCs	(23)	1	Concomitant synthesis of glass matrix and NPs: sol-gel method combined with heat treatment in a suitable atmosphere	Photocatalytic degradation of organic pollutants	[251]
In₂O₃ NCs@silica glass	Silica glass	In₂O₃ NCs	(54)	3		Photocatalytic degradation of organic pollutants	[251]
Au NPs@sodium borosilicate glass	Sodium borosilicate glass (75 wt.% SiO₂, 20 wt.% B₂O₃, and 5 wt.% Na₂O)	Au NPs	2.82?9.97 (5.48)	0.25	Concomitant synthesis of glass matrix and NPs: sol-gel method combined with heat treatment in a suitable atmosphere	NLO devices: χ⁽³⁾_{(800 nm)} = 1.7 × 10^?14 esu	[252]
Cu_3.8Ni@sodium borosilicate glass	Sodium borosilicate glass (72.88 wt.% SiO₂, 21.38 wt.% B₂O₃, and 5.74 wt.% Na₂O)	Cu_3.8Ni alloy NPs	15?40 (27.5)	1.5	Concomitant synthesis of glass matrix and NPs: sol-gel method combined with heat treatment in a suitable atmosphere	NLO devices: χ⁽³⁾_{(800 nm)} = 4.92 × 10^?11 esu	[253]
Au NP/Ni NP@sodium borosilicate glass	Sodium borosilicate glass (75 wt.% SiO₂, 20 wt.% B₂O₃, and 5 wt.% Na₂O)	Au NPs and Ni NPs	8 nm Au NPs, 2 nm Ni NPs	2 wt.% Au, 1 wt.% Ni	Concomitant synthesis of glass matrix and NPs: sol-gel method combined with heat treatment in a suitable atmosphere	NLO devices: χ⁽³⁾_{(800 nm)} = 2.31 × 10^?12 esu	[254]
Au NP/NiO NP@sodium borosilicate glass	Sodium borosilicate glass (75 wt.% SiO₂, 20 wt.% B₂O₃, and 5 wt.% Na₂O)	Au NPs and NiO NPs	7 nm Au NPs, 7 nm NiO NPs	2 wt.% Au, 1 wt.% NiO	Concomitant synthesis of glass matrix and NPs: sol-gel method combined with heat treatment in a suitable atmosphere	NLO devices: χ⁽³⁾_{(800 nm)} = 1.81 × 10^?13 esu	[254]
Au NPs/Cu NPs@sodium borosilicate glass (1)	Sodium borosilicate glass (96.7 wt.% SiO₂, 2.7 wt.% B₂O₃, and 0.6 wt.% Na₂O)	Au NPs and Cu NPs	12.89 nm Au NPs, 12.89 nm Cu NPs	0.25 wt.% Au, 0.75 wt.% Cu	Concomitant synthesis of glass matrix and NPs: sol-gel method combined with heat treatment in a suitable atmosphere	NLO devices: χ⁽³⁾_{(800 nm)} = 3.1 × 10^?12 esu	[255]
Au NPs/Cu NPs@sodium borosilicate glass (2)	Sodium borosilicate glass (96.7 wt.% SiO₂, 2.7 wt.% B₂O₃, and 0.6 wt.% Na₂O)	Au NPs and Cu NPs	18.08 nm Au NPs, 18.08 nm Cu NPs	0.25 wt.% Au, 0.75 wt.% Cu	Concomitant synthesis of glass matrix and NPs: sol-gel method combined with heat treatment in a suitable atmosphere	NLO devices: χ⁽³⁾_{(800 nm)} =5.4 × 10^?12 esu
Au NPs/Cu NPs@sodium borosilicate glass (3)	Sodium borosilicate glass (96.7 wt.% SiO₂, 2.7 wt.% B₂O₃, and 0.6 wt.% Na₂O)	Au NPs and Cu NPs	22.3 nm Au NPs, 22.3 nm Cu NPs	0.25 wt.% Au, 0.75 wt.% Cu	Concomitant synthesis of glass matrix and NPs: sol-gel method combined with heat treatment in a suitable atmosphere	NLO devices: χ⁽³⁾_{(800 nm)} = 4.4 × 10^?12 esu
Cu NPs@borosilicate glass^m)	Sodium borosilicate glass (75 wt.% SiO₂, 20 wt.% B₂O₃, and 5 wt.% Na₂O)	Cu NPs	9?34 (18.8)	2	Concomitant synthesis of glass matrix and NPs: sol-gel method combined with heat treatment in a suitable atmosphere	NLO devices: χ⁽³⁾_{(800 nm)} = 6.4 × 10^?14 esu	[14]
Cu₂O NCs@borosilicate glassⁿ⁾	Sodium borosilicate glass (75 wt.% SiO₂, 20 wt.% B₂O₃, and 5 wt.% Na₂O)	Cu₂O NCs	1?6 (3.12)	2	Concomitant synthesis of glass matrix and NPs: sol-gel method combined with heat treatment in a suitable atmosphere	NLO devices: χ⁽³⁾_{(800 nm)} = 1.6 × 10^?14 esu
CuO NCs@borosilicate glass^o)	Sodium borosilicate glass (75 wt.% SiO₂, 20 wt.% B₂O₃, and 5 wt.% Na₂O)	CuO NCs	1?5 (2.24)	2	Concomitant synthesis of glass matrix and NPs: sol-gel method combined with heat treatment in a suitable atmosphere	NLO devices: χ⁽³⁾_{(800 nm)} = 2.6 × 10^?14 esu
Au NPs/Ag NPs@silica glass	Silica glass	Au NPs and Ag NPs	3.7?63 (22)	?	Sol-gel technique combined with NP or NP precursors impregnation: sol-gel method and loading of NPs	Art	[156]
AuAg@silica glass	Silica glass	AuAg alloy NPs	5.6?51.9 (16)	?	Sol-gel technique combined with NP or NP precursors impregnation: sol-gel method and loading of NPs	Art	[156]
Au NPs@silica glass	Silica glass	Au NPs	10?30	?	Sol-gel technique combined with NP or NP precursors impregnation: sol-gel method and loading of NPs	NLO devices: β_{(532 nm)} = ?1.37 × 10^?10 m·W^?1	[256]
Sm₂O₃ NPs@borosilicate glass	Borosilicate glass (85.17 wt.% SiO₂, 14.83 wt.% B₂O₃)	Sm₂O₃ NPs	(2.7)	5.12	Sol-gel technique combined with NP or NP precursors impregnation: sol-gel method and loading of NP precursors	High-density optical storage, undersea communication, and color displays	[257]
Sm₂O₃ NPs@sodium borosilicate glass	Sodium borosilicate glass (77.80 wt.% SiO₂, 13.54 wt.% B₂O₃, and 8.65 wt.% Na₂O)	Sm₂O₃ NPs	(4.1)	4.44	Sol-gel technique combined with NP or NP precursors impregnation: sol-gel method and loading of NP precursors		[257]

Tab.3 GNCs prepared by sol-gel techniques [14,15,241–257]

Fig.15 (a) TEM image of Sb NPs embedded in sodium borosilicate glass. (b) Size distribution of Sb NPs in the glass matrix. (c) HRTEM of Sb NPs@sodium borosilicate glass. (d) SAED image of Sb NPs@sodium borosilicate glass. Reproduced with permission from Ref. [249] (Copyright 2014 Elsevier).

Fig.16 (a) TEM image of Au NPs embedded in sodium borosilicate glass. (b) Size distribution of Au NPs in the glass matrix. (c) HRTEM of Au NPs@sodium borosilicate glass. (d) SAED image of Au NPs@sodium borosilicate glass. Reproduced with permission from Ref. [252] (Copyright 2015 Springer Nature).

Fig.17 TEM images of (a) red GNC, (b) green GNC, and (c) blue GNC. HRTEM images of (d) red GNC, (e) green GNC, and (f) blue GNC. Size distribution images of (g) red GNC, (h) green GNC, and (i) blue GNC. Photographs of as-obtained (j) red GNC, (k) green GNC, and (l) blue GNC. Reproduced with permission from Ref. [14] (Copyright 2015 American Chemical Society).

Composite	Host matrix	Reinforcement	Size of NPs (min?max (mean))/nm	Ion implantation technique	Application	Ref.
Au NPs@silica glass	Silica glass	Au NPs	(2)	Single implantation: ion implantation — Au ions of 190 keV, ion fluence (4 × 10¹⁶ ion·cm^?2), flux (2 μA·cm^?2)	?	[282]
Au NPs@silica glass	Silica glass	Au NPs	(3.6)	Single implantation: ion implantation — Au ions of 190 keV, ion fluence (4 × 10¹⁶ ion·cm^?2), flux (2 μA·cm^?2); annealing (at 900 °C for 1 h)
Au NPs@silica glass	Silica glass	Au NPs	(5.6)	Single implantation: ion implantation — Au ions of 190 keV, ion fluence (4 × 10¹⁶ ion·cm^?2), flux (2 μA·cm^?2); annealing (at 900 °C for 3 h)
Au NPs@silica glass	Silica glass	Au NPs	(12.6)	Single implantation: ion implantation — Au ions of 190 keV, ion fluence (4 × 10¹⁶ ion·cm^?2), flux (2 μA·cm^?2); annealing (at 900 °C for 12 h)
Ag NPs@silica glass	Silica glass	Ag NPs	(7.7)	Single implantation: ion implantation — Ag ions of 1 MeV, ion fluence (5 × 10¹⁶ ion·cm^?2), flux (1 μA·cm^?2)	?	[283]
Ag NPs@silica glass	Silica glass	Ag NPs	(2.7)	Single implantation: ion implantation — Ag ions of 1 MeV, ion fluence (5 × 10¹⁶ ion·cm^?2), flux (1 μA·cm^?2); ion implantation — Si ions of 9.4 MeV, ion fluence (1 × 10¹⁴?8 × 10¹⁵ ion·cm^?2)	?	[283]
Ag NPs@chalcohalide glass	Chalcohalide glass (48.80 wt.% GeS₂, 36.04 wt.% Ga₂S₃, and 15.16 wt.% KBr)	Ag NPs	(100)	Single implantation: ion implantation — Ag ions of 200 MeV, ion fluence (1 × 10¹⁶ ion·cm^?2)	NLO devices: χ⁽³⁾_{(800 nm)} = 2.6 × 10^?13 esu	[284]
Ag NPs@chalcohalide glass	Chalcohalide glass (48.80 wt.% GeS₂, 36.04 wt.% Ga₂S₃, and 15.16 wt.% KBr)	Ag NPs	(150)	Single implantation: ion implantation — Ag ions of 200 MeV, ion fluence (5 × 10¹⁶ ion·cm^?2)	NLO devices: χ⁽³⁾_{(800 nm)} = 2.8 × 10^?13 esu
Ag NPs@chalcohalide glass	Chalcohalide glass (48.80 wt.% GeS₂, 36.04 wt.% Ga₂S₃, and 15.16 wt.% KBr)	Ag NPs	(200)	Single implantation: ion implantation — Ag ions of 200 MeV, ion fluence (1 × 10¹⁷ ion·cm^?2)	NLO devices: χ⁽³⁾_{(800 nm)} = 3.3 × 10^?13 esu
Ag NPs@chalcohalide glass	Chalcohalide glass (48.80 wt.% GeS₂, 36.04 wt.% Ga₂S₃, and 15.16 wt.% KBr)	Ag NPs	(300)	Single implantation: ion implantation — Ag ions of 200 MeV, ion fluence (2 × 10¹⁷ ion·cm^?2)	NLO devices: χ⁽³⁾_{(800 nm)} = 1.4 × 10^?13 esu
Ag NPs@silica glass	Silica glass	Ag NPs	(1.2)	Single implantation: ion implantation — Ag ions of 330 keV, ion fluence (1 × 10¹⁶ ion·cm^?2); annealing (at 600 °C for 1 h)	?	[285]
Ag NPs@silica glass	Silica glass	Ag NPs	(1)	Single implantation: ion implantation — Ag ions of 1.2 MeV, ion fluence (1 × 10¹⁶ ion·cm^?2); annealing (at 600 °C for 1 h)
Ag NPs@silica glass	Silica glass	Ag NPs	(1)	Single implantation: ion implantation — Ag ions of 1.7 MeV, ion fluence (1 × 10¹⁶ ion·cm^?2); annealing (at 600 °C for 1 h)
Au NPs@silica glass	Silica glas	Au NPs	(2.84)	Single implantation: ion implantation — Au ions of 60 keV, ion fluence (3 × 10¹⁶ ion·cm^?2), flux (1.5 μA·cm^?2)	Optoelectronics	[286]
Au NPs@silica glass	Silica glas	Au NPs	(2.66)	Single implantation: ion implantation — Au ions of 60 keV, ion fluence (4 × 10¹⁶ ion·cm^?2), flux (1.5 μA·cm^?2)
Au NPs@silica glass	Silica glas	Au NPs	(3.18)	Single implantation: ion implantation — Au ions of 60 keV, ion fluence (5 × 10¹⁶ ion·cm^?2), flux (1.5 μA·cm^?2)
Au NPs@silica glass	Silica glas	Au NPs	(3.02)	Single implantation: ion implantation — Au ions of 60 keV, ion fluence (6 × 10¹⁶ ion·cm^?2), flux (1.5 μA·cm^?2)
Au NPs@silica glass	Silica glas	Au NPs	(9.14)	Single implantation: ion implantation — Au ions of 60 keV, ion fluence (7 × 10¹⁶ ion·cm^?2); flux (1.5 μA·cm^?2)
Au NPs@silica glass	Silica glas	Au NPs	(9.98)	Single implantation: ion implantation — Au ions of 60 keV, ion fluence (8 × 10¹⁶ ion·cm^?2), flux (1.5 μA·cm^?2)
Au NPs@silica glass	Silica glas	Au NPs	(11.68)	Single implantation: ion implantation — Au ions of 60 keV, ion fluence (9 × 10¹⁶ ion·cm^?2), flux (1.5 μA·cm^?2)
Au NPs@borate glass	Borate glass (10.66 wt.% B₂O₃, 67.12 wt.% PbO, 9.62 wt.% GeO₂, 10.71 wt.% Bi₂O₃, and 1.89 wt.% Pr₂O₃)	Au NPs	(2.8)	Single implantation: Melt-quenching for glass preparation (melting at 1250 °C for 1 h); annealing (at 330 °C for 2 h); ion implantation — Au ions of 300 keV, ion fluence (1 × 10¹⁶ ion·cm^?2); annealing (at 330 °C for 12 h)	Gain media for amplifiers in optical telecommunication windows	[287]
Cu NPs@silica glass	Silica glass	Cu NPs	(20)	Single implantation: ion implantation — Cu ions of 40 keV, ion fluence (5 × 10¹⁶ ion·cm^?2), flux (5 μA·cm^?2)	?	[288]
Cu NPs@silica glass	Silica glass	Cu NPs	6?10	Single implantation: ion implantation — Cu ions of 200 keV, ion fluence (3 × 10¹⁶ ion·cm^?2); annealing (at 400 °C for 1 h)	NLO devices: χ⁽³⁾_{(532 nm)} = 1.5 × 10^?8 esu	[289]
Au NPs@silica glass	Silica glass	Au NPs	6?10	Single implantation: ion implantation — Au ions of 1.5 MeV, ion fluence (1 × 10¹⁷ ion·cm^?2); annealing (at 400 °C for 1 h)	NLO devices: χ⁽³⁾_{(532 nm)} = ?3.7 × 10^?12 esu
Cu NPs@silica glass	Silica glass	Cu NPs	1?15 (5.6)	Single implantation: ion implantation — Cu ions of 180 keV, ion fluence (1 × 10¹⁷ ion·cm^?2), flux (1.5 μA·cm^?2)	NLO devices: χ⁽³⁾_{(532 nm)} = ?2.1 × 10^?7 esu, χ⁽³⁾_{(1064 nm)} = ?1.2 × 10^?7 esu	[290]
Ag NPs@silica glass	Silica glass	Ag NPs	35?48	Multiple implantation: ion implantation — Ag ions of 200 keV, ion fluence (5 × 10¹⁶ ion·cm^?2), flux (1 μA·cm^?2); ion implantation — Cu ions of 110 keV, ion fluence (5 × 10¹⁶ ion·cm^?2), flux (1.5 μA·cm^?2)	?	[291]
Ag NPs/Ni NPs@silica glass	Silica glass	Ag NPs and Ni NPs	0.5?2 nm Ag NPs, 0.5?4 nm Ni NPs	Multiple implantation:ion on implantation — Ni ions of 60 keV, ion fluence (5 × 10¹⁶ ion·cm^?2), flux (4 μA·cm^?2); ion implantation — Ag ions of 70 keV, ion fluence (5 × 10¹⁶ ion·cm^?2), flux (4 μA·cm^?2); annealing (at 600 °C for 1 h)	Optoelectronics, optical sensors, and antibacterial materials	[292]
Ag NPs@silica glass	Silica glass	Ag NPs	3?17	Single implantation: ion implantation — Ag ions of 35 keV, ion fluence (5 × 10¹⁶ ion·cm^?2), flux (4 μA·cm^?2)	Optoelectronics, optical sensors, and antibacterial materials	[293]
Ag NPs@silica glass	Silica glass	Ag NPs	4?8	Multiple implantation: ion implantation — Zn ions of 50 keV, ion fluence (5 × 10¹⁶ ion·cm^?2), flux (4 μA·cm^?2); ion implantation — Ag ions of 35 keV, ion fluence (5 × 10¹⁶ ion·cm^?2), flux (4 μA·cm^?2)
Ag NPs/Zn NPs/AgZn NPs@silica glass	Silica glass	Ag NPs, Zn NPs and AgZn alloy NPs	2?12	Multiple implantation: ion implantation — Ag ions of 35 keV, ion fluence (5 × 10¹⁶ ion·cm^?2), flux (4 μA·cm^?2); ion implantation — Zn ions of 50 keV, ion fluence (5 × 10¹⁶ ion·cm^?2), flux (4 μA·cm^?2)

Tab.4 GNCs prepared by ion implantation techniques [282?293]

Fig.19 TEM images of Ag NPs within silica glass (a) before and (b) after Si ion-irradiation. NP size distribution histograms are shown as insets. Reproduced with permission from Ref. [283] (Copyright 2014 Elsevier).

Fig.20 Cross-sectional bright-field TEM images of (a) the as-implanted and the annealed for (c) 1 h, (e) 3 h, and (g) 12 h GNCs. Au NPs size distribution in (b) the as-implanted and the annealed for (d) 1 h, (f) 3 h, and (h) 12 h GNCs. Reproduced with permission from Ref. [282] (Copyright 2002 AIP Publishing).

Fig.21 (a) Cross-sectional TEM image, (b) SAED result, and (c) Ag NP size distribution of the GNC prepared by Ag⁺ ion implantation. (d) Cross-sectional TEM image, (e) SAED result, and (f) Ag NP size distribution of the GNC prepared by Zn²⁺ ion implantation and Ag⁺ ion post-implantation. (g) Cross-sectional TEM image, (h) SAED result, and (i) Ag NP size distribution of the GNC prepared by Ag⁺ ion implantation and Zn²⁺ ion post-implantation. Reproduced with permission from Ref. [293] (Copyright 2013 AIP Publishing).

Fig.22 Schematic illustration of the annealing processes in a GNC formed by Cu⁺ ion implantation and Zn²⁺ ion post-implantation (fluence of 5 × 10¹⁶ ions·cm^?2): (a) CuZn alloy NP; (b) Zn diffusion-driven realloying process; (c) Zn diffusion-driven formation of the Cu-rich core and Zn-rich shell structure; (d) Cu core and Zn shell NP. Reproduced with permission from Ref. [308] (Copyright 2013 American Chemical Society).

Fig.23 (a) Schematic illustration of thermally assisted ion-exchange. (b) The monovalent cation A is introduced into the glass matrix, which contains the monovalent cation B, by an interphase chemical potential gradient. To maintain charge neutrality, the monovalent cation B is released into the molten salt solution. (c) Schematic illustration of electric field-assisted ion-exchange.

Composite	Host matrix	Reinforcement	Size of NPs (min-max (mean))/nm	Ion-exchange technique	Application	Ref.
Ag NPs@borosilicate glass	Borosilicate glass (52.70 wt.% SiO₂, 11.11 wt.% B₂O₃, 24.71 wt.% Na₂O, 8.13 wt.% Al₂O₃, and 3.35 wt.% NaF)	Ag NPs	(2.0 ± 1.00)	Direct formation of NPs: ion-exchange — AgNO₃:NaNO₃ melt (0.99:99.01 wt.%), 310 °C for 1 h	Photoluminescence	[324]
Ag NPs@borosilicate glass	Borosilicate glass (52.70 wt.% SiO₂, 11.11 wt.% B₂O₃, 24.71 wt.% Na₂O, 8.13 wt.% Al₂O₃, and 3.35 wt.% NaF)	Ag NPs	(4.2 ± 2.2)	Direct formation of NPs: ion-exchange — AgNO₃:NaNO₃ melt (3.84:96.16 wt.%), 310 °C for 1 h
Ag NPs@borosilicate glass	Borosilicate glass (52.70 wt.% SiO₂, 11.11 wt.% B₂O₃, 24.71 wt.% Na₂O, 8.13 wt.% Al₂O₃, and 3.35 wt.% NaF)	Ag NPs	(6.2 ± 2.5)	Direct formation of NPs: ion-exchange — AgNO₃:NaNO₃ melt (16.66:83.34 wt.%), 310 °C for 1 h
Ag NPs@silicate glass	Silicate glass (40.45 wt.% SiO₂, 15.26 wt.% Al₂O₃, 13.91 wt.% Na₂O, 6.03 wt.% MgO, and 24.35 wt.% ZnO)	Ag NPs	(1.5 ± 1)	Direct formation of NPs: ion-exchange — AgNO₃:NaNO₃ melt (1.98:98.02 wt.%), 350 °C for 1 h	?	[325]
Ag NPs@silicate glass	Silicate glass (40.45 wt.% SiO₂, 15.26 wt.% Al₂O₃, 13.91 wt.% Na₂O, 6.03 wt.% MgO, and 24.35 wt.% ZnO)	Ag NPs	(2.0 ± 1.1)	Direct formation of NPs: ion-exchange — AgNO₃:NaNO₃ melt (13.08:86.92 wt.%), 350 °C for 1 h
Ag NPs@silicate glass	Silicate glass (40.45 wt.% SiO₂, 15.26 wt.% Al₂O₃, 13.91 wt.% Na₂O, 6.03 wt.% MgO, and 24.35 wt.% ZnO)	Ag NPs	(2.2 ± 1.1)	Direct formation of NPs: ion-exchange — AgNO₃:NaNO₃ melt (33.32:66.68 wt.%), 350 °C for 1 h
Ag NPs@silicate glass	Silicate glass (40.45 wt.% SiO₂, 15.26 wt.% Al₂O₃, 13.91 wt.% Na₂O, 6.03 wt.% MgO, and 24.35 wt.% ZnO)	Ag NPs	(2.3 ± 1.8)	Direct formation of NPs: ion-exchange — AgNO₃:NaNO₃ melt (66.65:33.35 wt.%), 350 °C for 1 h
Ag NPs@silicate glass	Silicate glass (40.45 wt.% SiO₂, 15.26 wt.% Al₂O₃, 13.91 wt.% Na₂O, 6.03 wt.% MgO, and 24.35 wt.% ZnO)	Ag NPs	(1.6 ± 1.0)	Direct formation of NPs: ion-exchange — AgNO₃:NaNO₃ melt (13.08:86.92 wt.%), 380 °C for 15 min
Ag NPs@silicate glass	Silicate glass (40.45 wt.% SiO₂, 15.26 wt.% Al₂O₃, 13.91 wt.% Na₂O, 6.03 wt.% MgO, and 24.35 wt.% ZnO)	Ag NPs	(2.0 ± 1.0)	Direct formation of NPs: ion-exchange — AgNO₃:NaNO₃ melt (13.08:86.92 wt.%), 380 °C for 1.5 h
Ag NPs@silicate glass	Silicate glass (40.45 wt.% SiO₂, 15.26 wt.% Al₂O₃, 13.91 wt.% Na₂O, 6.03 wt.% MgO, and 24.35 wt.% ZnO)	Ag NPs	(2.5 ± 1.2)	Direct formation of NPs: ion-exchange — AgNO₃:NaNO₃ melt (13.08:86.92 wt.%), 380 °C for 4 h
Ag NPs@silicate glass	Silicate glass (40.45 wt.% SiO₂, 15.26 wt.% Al₂O₃, 13.91 wt.% Na₂O, 6.03 wt.% MgO, and 24.35 wt.% ZnO)	Ag NPs	(1.8 ± 1.2)	Direct formation of NPs: ion-exchange — AgNO₃:NaNO₃ melt (13.08:86.92 wt.%), 300 °C for 1 h	?	[325]
Ag NPs@silicate glass	Silicate glass (40.45 wt.% SiO₂, 15.26 wt.% Al₂O₃, 13.91 wt.% Na₂O, 6.03 wt.% MgO, and 24.35 wt.% ZnO)	Ag NPs	(2.4 ± 1.2)	Direct formation of NPs: ion-exchange — AgNO₃:NaNO₃ melt (13.08:86.92 wt.%), 400 °C for 1 h	?	[325]
Ag NPs@silicate glass	Silicate glass (39.41 wt.% SiO₂, 14.86 wt.% Al₂O₃, 13.55 wt.% Na₂O, 5.88 wt.% MgO, 23.73 wt.% ZnO, and 2.57 wt.% Eu₂O₃)	Ag NPs	(3.0 ± 1.6)	Direct formation of NPs: ion-exchange — AgNO₃:NaNO₃ melt (1.98:98.02 wt.%), 380 °C for 1 h	Photoluminescence	[325]
Ag NPs@silicate glass	Silicate glass (39.41 wt.% SiO₂, 14.86 wt.% Al₂O₃, 13.55 wt.% Na₂O, 5.88 wt.% MgO, 23.73 wt.% ZnO, and 2.57 wt.% Eu₂O₃)	Ag NPs	(3.3 ± 1.2)	Direct formation of NPs: ion-exchange — AgNO₃:NaNO₃ melt (13.08:86.92 wt.%), 380 °C for 1 h
Ag NPs@silicate glass	Silicate glass (39.41 wt.% SiO₂, 14.86 wt.% Al₂O₃, 13.55 wt.% Na₂O, 5.88 wt.% MgO, 23.73 wt.% ZnO, and 2.57 wt.% Eu₂O₃)	Ag NPs	(3.4 ± 1.5)	Direct formation of NPs: ion-exchange — AgNO₃:NaNO₃ melt (33.32:66.68 wt.%), 380 °C for 1 h
Ag NPs@silicate glass	Silicate glass (39.41 wt.% SiO₂, 14.86 wt.% Al₂O₃, 13.55 wt.% Na₂O, 5.88 wt.% MgO, 23.73 wt.% ZnO, and 2.57 wt.% Eu₂O₃)	Ag NPs	(3.6 ± 1.4)	Direct formation of NPs: ion-exchange — AgNO₃:NaNO₃ melt (66.65:33.35 wt.%), 380 °C for 1 h
Ag NPs@Corning 0211 glass	Corning 0211 glass	Ag NPs	(10)	Direct formation of NPs: ion-exchange — AgNO₃:NaNO₃:KNO₃ melt (8.77:41.66:49.57 wt.%), 300 °C for 6 h; Al film evaporation; immersion in a KNO₃ salt at 400 °C for 2 h	NLO devices: β_{(800 nm)} = 1.4 × 10^?14 cm²·W^?1	[326]
Ag NPs@silicate glass	Silicate glass (71.58 wt.% SiO₂, 14.36 wt.% Na₂O, 6.59 wt.% CaO, 2.67 wt.% MgO, 3.21 wt.% Al₂O₃, 0.94 wt.% K₂O, 0.4 wt.% SO₃, and 0.26 wt.% Fe₂O₃)	Ag NPs	(2.8 ± 1)	Thermal annealing in air: ion-exchange — AgNO₃:NaNO₃ melt (13.08:86.92 wt.%), 370 °C for few min; post ion-exchange annealing — air atmosphere (450 °C for 1 h)	Photoluminescence	[327]
Ag NPs@silicate glass	Silicate glass (71.58 wt.% SiO₂, 14.36 wt.% Na₂O, 6.59 wt.% CaO, 2.67 wt.% MgO, 3.21 wt.% Al₂O₃, 0.94 wt.% K₂O, 0.4 wt.% SO₃, and 0.26 wt.% Fe₂O₃)	Ag NPs	(3.3 ± 1.2)	Thermal annealing in air: ion-exchange — AgNO₃:NaNO₃ melt (13.08:86.92 wt.%), 370 °C for few min; post ion-exchange annealing — air atmosphere (500 °C for 1 h)
Ag NPs@silicate glass	Silicate glass (71.58 wt.% SiO₂, 14.36 wt.% Na₂O, 6.59 wt.% CaO, 2.67 wt.% MgO, 3.21 wt.% Al₂O₃, 0.94 wt.% K₂O, 0.4 wt.% SO₃, and 0.26 wt.% Fe₂O₃)	Ag NPs	(4.0 ± 1.5)	Thermal annealing in air: ion-exchange — AgNO₃:NaNO₃ melt (13.08:86.92 wt.%), 370 °C for few min; post ion-exchange annealing — air atmosphere (550 °C for 1 h)
Ag NPs@silicate glass	Silicate glass (71.58 wt.% SiO₂, 14.36 wt.% Na₂O, 6.59 wt.% CaO, 2.67 wt.% MgO, 3.21 wt.% Al₂O₃, 0.94 wt.% K₂O, 0.4 wt.% SO₃, and 0.26 wt.% Fe₂O₃)	Ag NPs	(2.9)	Thermal annealing in air: ion-exchange — AgNO₃:NaNO₃ melt (13.08:86.92 wt.%), 370 °C for 2 min; post ion-exchange annealing — air atmosphere (500 °C for 1 h)	Photoluminescence	[328]
Ag NPs@silicate glass	Silicate glass (71.58 wt.% SiO₂, 14.36 wt.% Na₂O, 6.59 wt.% CaO, 2.67 wt.% MgO, 3.21 wt.% Al₂O₃, 0.94 wt.% K₂O, 0.4 wt.% SO₃, and 0.26 wt.% Fe₂O₃)	Ag NPs	(4.4)	Thermal annealing in air: ion-exchange — AgNO₃:NaNO₃ melt (13.08:86.92 wt.%), 370 °C for 2 min; post ion-exchange annealing — air atmosphere (550 °C for 1 h)
Ag NPs@silicate glass	Silicate glass (71.58 wt.% SiO₂, 14.36 wt.% Na₂O, 6.59 wt.% CaO, 2.67 wt.% MgO, 3.21 wt.% Al₂O₃, 0.94 wt.% K₂O, 0.4 wt.% SO₃, and 0.26 wt.% Fe₂O₃)	Ag NPs	(7.2)	Thermal annealing in air: ion-exchange — AgNO₃:NaNO₃ melt (13.08:86.92 wt.%), 370 °C for 2 min; post ion-exchange annealing — air atmosphere (600 °C for 1 h)
Ag NPs@soda-lime silicate glass	Soda-lime silicate glass (71.63 wt.% SiO₂, 2.08 wt.% Al₂O₃, 0.5 wt.% Fe₂O₃, 0.19 wt.% TiO₂, 0.59 wt.% SO₃, 6.27 wt.% CaO, 2.8 wt.% MgO, 15.4 wt.% Na₂O, and 0.53 wt.% K₂O)	Ag NPs	(1.8 ± 1.1)	Thermal annealing in air: ion-exchange — AgNO₃:NaNO₃ melt (33.33:66.66 wt.%), 360 °C for 1 h; post ion-exchange annealing — air atmosphere (450 °C for 30 min)	?	[329]
Ag NPs@soda-lime silicate glass	Soda-lime silicate glass (71.63 wt.% SiO₂, 2.08 wt.% Al₂O₃, 0.5 wt.% Fe₂O₃, 0.19 wt.% TiO₂, 0.59 wt.% SO₃, 6.27 wt.% CaO, 2.8 wt.% MgO, 15.4 wt.% Na₂O, and 0.53 wt.% K₂O)	Ag NPs	(1.9 ± 1.2)	Thermal annealing in air: ion-exchange — AgNO₃:NaNO₃ melt (33.33:66.66 wt.%), 360 °C for 1 h; post ion-exchange annealing — air atmosphere (500 °C for 30 min)
Ag NPs@soda-lime silicate glass	Soda-lime silicate glass (71.63 wt.% SiO₂, 2.08 wt.% Al₂O₃, 0.5 wt.% Fe₂O₃, 0.19 wt.% TiO₂, 0.59 wt.% SO₃, 6.27 wt.% CaO, 2.8 wt.% MgO, 15.4 wt.% Na₂O, and 0.53 wt.% K₂O)	Ag NPs	(2.2 ± 0.6)	Thermal annealing in air: ion-exchange — AgNO₃:NaNO₃ melt (33.33:66.66 wt.%), 360 °C for 1 h; post ion-exchange annealing — air atmosphere (550 °C for 30 min)
Ag NPs@soda-lime silicate glass	Soda-lime silicate glass (73.65 wt.% SiO₂, 14.64 wt.% Na₂O, 3.2 wt.% Al₂O₃, 7.5 wt.% CaO, and 1.0 wt.% MgO)	Ag NPs	(2)	Thermal annealing in air: ion-exchange — AgNO₃:NaNO₃ melt (3.92:96.08 wt.%), 350 °C for 10 min; post ion-exchange annealing — air atmosphere (600 °C for 45 h)	?	[330]
Ag NPs@silicate glass	Silicate glass (5.73 wt.% Na₂O, 7.52 wt.% ZnO, 9.42 wt.% Al₂O₃, 5.55 wt.% SiO₂, 36.42 wt.% Yb₂O₃, and 35.36 wt.% Er₂O₃)	Ag NPs	3?10	Thermal annealing in air: ion-exchange — AgNO₃:NaNO₃:KNO₃ melt (14:45:41 wt.%), 280 °C for 50 min	Photoluminescence	[79]
Ag NPs@silicate glass	Silicate glass (5.75 wt.% Na₂O, 7.55 wt.% ZnO, 9.46 wt.% Al₂O₃, 5.58 wt.% SiO₂, 36.58 wt.% Yb₂O₃, and 35.07 wt.% Ho₂O₃)	Ag NPs	10?60
Ag NPs@silicate glass	Silicate glass (5.71 wt.% Na₂O, 7.50 wt.% ZnO, 9.39 wt.% Al₂O₃, 5.54 wt.% SiO₂, 36.31 wt.% Yb₂O₃, and 35.55 wt.% Tm₂O₃)	Ag NPs	10?40
Cu NPs@silicate glass	Borosilicate glass (72.0 wt.% SiO₂, 14.0 wt.% Na₂O, 0.6 wt.% K₂O, 7.1 wt.% CaO, 4.0 wt.% MgO, 1.9 wt.% Al₂O₃, 0.1 wt.% Fe₂O₃, and 0.3 wt.% SO₃)	Cu NPs	(7)	Thermal annealing in air: ion-exchange — CuSO₄·5H₂O:Na₂SO₄ melt (67.36:32.64 wt.%), 590 °C for 2 min; post ion-exchange annealing — air atmosphere (450 °C for 1 h)	NLO devices	[331]
Cu NPs@silicate glass	Borosilicate glass (72.0 wt.% SiO₂, 14.0 wt.% Na₂O, 0.6 wt.% K₂O, 7.1 wt.% CaO, 4.0 wt.% MgO, 1.9 wt.% Al₂O₃, 0.1 wt.% Fe₂O₃, and 0.3 wt.% SO₃)	Cu NPs	(7)	Thermal annealing in air: ion-exchange — CuSO₄·5H₂O:Na₂SO₄ melt (67.36:32.64 wt.%), 590 °C for 2 min; post ion-exchange annealing — air atmosphere (500 °C for 1 h)
Cu NPs@silicate glass	Borosilicate glass (72.0 wt.% SiO₂, 14.0 wt.% Na₂O, 0.6 wt.% K₂O, 7.1 wt.% CaO, 4.0 wt.% MgO, 1.9 wt.% Al₂O₃, 0.1 wt.% Fe₂O₃, and 0.3 wt.% SO₃)	Cu NPs	(8)	Thermal annealing in air: ion-exchange — CuSO₄·5H₂O:Na₂SO₄ melt (67.36:32.64 wt.%), 590 °C for 2 min; post ion-exchange annealing — air atmosphere (550 °C for 1 h)
Cu NPs@silicate glass	Borosilicate glass (72.0 wt.% SiO₂, 14.0 wt.% Na₂O, 0.6 wt.% K₂O, 7.1 wt.% CaO, 4.0 wt.% MgO, 1.9 wt.% Al₂O₃, 0.1 wt.% Fe₂O₃, and 0.3 wt.% SO₃)	Cu NPs	(9.5)	Thermal annealing in air: ion-exchange — CuSO₄·5H₂O:Na₂SO₄ melt (67.36:32.64 wt.%), 590 °C for 2 min; post ion-exchange annealing — air atmosphere (600 °C for 1 h)
Cu NPs@silicate glass	Borosilicate glass (72.0 wt.% SiO₂, 14.0 wt.% Na₂O, 0.6 wt.% K₂O, 7.1 wt.% CaO, 4.0 wt.% MgO, 1.9 wt.% Al₂O₃, 0.1 wt.% Fe₂O₃, and 0.3 wt.% SO₃)	Cu NPs	(10)	Thermal annealing in air: ion-exchange — CuSO₄·5H₂O:Na₂SO₄ melt (67.36:32.64 wt.%), 590 °C for 2 min; post ion-exchange annealing — air atmosphere (650 °C for 1 h)
Ag NPs@soda-lime silicate glass	Soda-lime silicate glass (69.36 wt.% SiO₂, 15.63 wt.% Na₂O, 3.04 wt.% Al₂O₃, 6.05 wt.% CaO, 3.41 wt.% MgO, 1.72 wt.% K₂O, 0.53 wt.% SO₃, and 0.27 wt.% TiO₂)	Ag NPs	2?4	Thermal annealing in air: ion-exchange — AgNO₃:NaNO₃ melt (0.2:99.8 wt.%), 320 °C for 30 min; post ion-exchange annealing — H₂ atmosphere (180 °C for 12 h)	NLO devices	[332]
Ag NPs@soda-lime silicate glass	Soda-lime silicate glass (69.36 wt.% SiO₂, 15.63 wt.% Na₂O, 3.04 wt.% Al₂O₃, 6.05 wt.% CaO, 3.41 wt.% MgO, 1.72 wt.% K₂O, 0.53 wt.% SO₃, and 0.27 wt.% TiO₂)	Ag NPs	4?6	Thermal annealing in air: ion-exchange — AgNO₃:NaNO₃ melt (0.2:99.8 wt.%), 320 °C for 30 min; post ion-exchange annealing — H₂ atmosphere (250 °C for 5 h)	NLO devices	[332]
Ag NPs@silicate glass	Silicate glass (69.59 wt.% SiO₂, 15.17 wt.% Na₂O, 5.08 wt.% MgO, 6.52 wt.% CaO, 1.73 wt.% Al₂O₃, 1.14 wt.% K₂O, and 0.78 wt.% SO₃)	Ag NPs	(1.6)	Thermal annealing in air: ion-exchange — AgNO₃:NaNO₃ melt (1.98:98.02 wt.%), 320 °C for 20 min; post ion-exchange annealing — air atmosphere (450 °C for 1 h)	?	[333]
Ag NPs@silicate glass	Silicate glass (69.59 wt.% SiO₂, 15.17 wt.% Na₂O, 5.08 wt.% MgO, 6.52 wt.% CaO, 1.73 wt.% Al₂O₃, 1.14 wt.% K₂O, and 0.78 wt.% SO₃)	Ag NPs	(2.0)	Thermal annealing in air: ion-exchange — AgNO₃:NaNO₃ melt (1.98:98.02 wt.%), 320 °C for 20 min; post ion-exchange annealing — air atmosphere (500 °C for 1 h)
Ag NPs@silicate glass	Silicate glass (69.59 wt.% SiO₂, 15.17 wt.% Na₂O, 5.08 wt.% MgO, 6.52 wt.% CaO, 1.73 wt.% Al₂O₃, 1.14 wt.% K₂O, and 0.78 wt.% SO₃)	Ag NPs	(2.6)	Thermal annealing in air: ion-exchange — AgNO₃:NaNO₃ melt (1.98:98.02 wt.%), 320 °C for 20 min; post ion-exchange annealing — air atmosphere (550 °C for 1 h)
Ag NPs@silicate glass	Silicate glass (69.59 wt.% SiO₂, 15.17 wt.% Na₂O, 5.08 wt.% MgO, 6.52 wt.% CaO, 1.73 wt.% Al₂O₃, 1.14 wt.% K₂O, and 0.78 wt.% SO₃)	Ag NPs	(2.7)	Irradiation: ion-exchange — AgNO₃:NaNO₃ melt (1.98:98.02 wt.%), 320 °C for 20 min; post ion-exchange annealing — air atmosphere (550 °C for 1 h); post ion-exchange irradiation (λ = 266 nm, number of pulses = 50, laser fluence = 18 J·cm^?2)
Ag NPs@silicate glass	Silicate glass (69.59 wt.% SiO₂, 15.17 wt.% Na₂O, 5.08 wt.% MgO, 6.52 wt.% CaO, 1.73 wt.% Al₂O₃, 1.14 wt.% K₂O, and 0.78 wt.% SO₃)	Ag NPs	(2.7)	Irradiation: ion-exchange — AgNO₃:NaNO₃ melt (1.98:98.02 wt.%), 320 °C for 20 min; post ion-exchange annealing — air atmosphere (550 °C for 1 h); post ion-exchange irradiation (λ = 266 nm, number of pulses = 200, laser fluence = 72 J·cm^?2)	?	[333]
Ag NPs@silicate glass	Silicate glass (69.59 wt.% SiO₂, 15.17 wt.% Na₂O, 5.08 wt.% MgO, 6.52 wt.% CaO, 1.73 wt.% Al₂O₃, 1.14 wt.% K₂O, and 0.78 wt.% SO₃)	Ag NPs	(2.6)	Irradiation: ion-exchange — AgNO₃:NaNO₃ melt (1.98:98.02 wt.%), 320 °C for 20 min; post ion-exchange annealing — air atmosphere (550 °C for 1 h); post ion-exchange irradiation (λ = 355 nm, number of pulses = 40, laser fluence = 14.4 J·cm^?2)
Ag NPs@silicate glass	Silicate glass (69.59 wt.% SiO₂, 15.17 wt.% Na₂O, 5.08 wt.% MgO, 6.52 wt.% CaO, 1.73 wt.% Al₂O₃, 1.14 wt.% K₂O, and 0.78 wt.% SO₃)	Ag NPs	(2.4)	Irradiation: ion-exchange — AgNO₃:NaNO₃ melt (1.98:98.02 wt.%), 320 °C for 20 min; post ion-exchange annealing — air atmosphere (550 °C for 1 h); post ion-exchange irradiation (λ = 355 nm, number of pulses = 200, laser fluence = 72 J·cm^?2)
Ag NPs@silicate glass	Silicate glass (69.59 wt.% SiO₂, 15.17 wt.% Na₂O, 5.08 wt.% MgO, 6.52 wt.% CaO, 1.73 wt.% Al₂O₃, 1.14 wt.% K₂O, and 0.78 wt.% SO₃)	Ag NPs	(2.6)	Irradiation: ion-exchange — AgNO₃:NaNO₃ melt (1.98:98.02 wt.%), 320 °C for 20 min; post ion-exchange annealing — air atmosphere (550 °C for 1 h); post ion-exchange irradiation (λ = 532 nm, number of pulses = 10, laser fluence = 3.6 J·cm^?2)
Ag NPs@silicate glass	Silicate glass (69.59 wt.% SiO₂, 15.17 wt.% Na₂O, 5.08 wt.% MgO, 6.52 wt.% CaO, 1.73 wt.% Al₂O₃, 1.14 wt.% K₂O, and 0.78 wt.% SO₃)	Ag NPs	(2.2)	Irradiation: ion-exchange — AgNO₃:NaNO₃ melt (1.98:98.02 wt.%), 320 °C for 20 min; post ion-exchange annealing — air atmosphere (550 °C for 1 h); post ion-exchange irradiation (λ = 532 nm, number of pulses = 50, laser fluence = 18 J·cm^?2)	?	[333]
Ag NPs@silicate glass	Silicate glass (69.59 wt.% SiO₂, 15.17 wt.% Na₂O, 5.08 wt.% MgO, 6.52 wt.% CaO, 1.73 wt.% Al₂O₃, 1.14 wt.% K₂O, and 0.78 wt.% SO₃)	Ag NPs	(1.9)	Irradiation: ion-exchange — AgNO₃:NaNO₃ melt (1.98:98.02 wt.%), 320 °C for 20 min; post ion-exchange annealing — air atmosphere (550 °C for 1 h); post ion-exchange irradiation (λ = 532 nm, number of pulses = 200, laser fluence = 72 J·cm^?2)	?	[333]
Ag NPs@soda-lime silicate glass	Soda-lime silicate glass (74.2 wt.% SiO₂, 14.3 wt.% Na₂O, 1.9 wt.% Al₂O₃, 8.1 wt.% CaO, and 1.5 wt.% MgO)	Ag NPs	3?8 (7)	Thermal annealing in air: ion-exchange — AgNO₃:NaNO₃ melt (3.92:96.08 wt.%), 320 °C for 10 min; post ion-exchange annealing—air atmosphere (600 °C for 45 h)	?	[334]
Ag NPs@soda-lime silicate glass	Soda-lime silicate glass (74.2 wt.% SiO₂, 14.3 wt.% Na₂O, 1.9 wt.% Al₂O₃, 8.1 wt.% CaO, and 1.5 wt.% MgO)	Ag NPs	(1)	Thermal annealing in air: ion-exchange — AgNO₃:NaNO₃ melt (3.92:96.08 wt.%), 320 °C for 10 min; post ion-exchange annealing — UV-laser irradiation, λ = 193 nm, pulse energy density (30 mJ?cm^?2), repetition frequency (10 Hz), pulse duration (20 ns), irradiation time (5 s)	?	[334]
Ag NPs@soda-lime silicate glass	Soda-lime silicate glass (74.2 wt.% SiO₂, 14.3 wt.% Na₂O, 1.9 wt.% Al₂O₃, 8.1 wt.% CaO, and 1.5 wt.% MgO)	Ag NPs	(2)	Thermal annealing in air: ion-exchange — AgNO₃:NaNO₃ melt (3.92:96.08 wt.%), 320 °C for 10 min; post ion-exchange annealing — UV-laser irradiation, λ =193 nm, pulse energy density (30 mJ?cm^-2), repetition frequency (10 Hz), pulse duration (20 ns), irradiation time (30 min)	?	[334]
Ag NPs@silicate glass	Silicate glass (71.92 wt.% SiO₂, 13.31 wt.% Na₂O, 4.15 wt.% MgO, 8.70 wt.% CaO, and 1.92 wt.% Al₂O₃)	Ag NPs	(4.93 ± 1.88)	Irradiation: ion-exchange — AgNO₃:NaNO₃ melt (20:80 wt.%), 350 °C for 30 s; post ion-exchange irradiation — Ar⁺ ions of 200 keV, ion fluence (5 × 10¹⁵ ion·cm^?2), flux (2 μA·cm^?2)	Optoelectronics	[335]
Ag NPs@soda-lime silicate glass	Soda-lime silicate glass	Ag NPs	(4.2)	Irradiation: ion-exchange — AgNO₃:NaNO₃ melt (2:98 wt.%), 400 °C for 2h; post ion-exchange irradiation — 100 kV electrons, flux (6.4 A·cm^?2)	?	[336]

Tab.5 GNCs prepared by ion-exchange techniques [79,324–336]

Fig.24 TEM images of GNCs prepared by ion-exchange in a molten bath with the AgNO₃:NaNO₃ molar ratio of (a) 1:1000, (b) 1:200, (c) 1:50, and (d) 1:10. The insets are the Ag NP size distribution histograms. Reproduced with permission from Ref. [324] (Copyright 2019 John Wiley and Sons).

Fig.26 Schematic illustration of the preparation of Ag NPs within a soda-lime silicate glass by ion-exchange and subsequent annealing. Reproduced with permission from Ref. [329] (Copyright 2012 American Chemical Society).

Fig.27 TEM images and corresponding Ag NP size distributions of the GNC treated (after ion-exchange) at (a)(b) 450 °C, (c)(d) 500 °C, (e)(f) 550 °C, (g)(h) 600 °C, and (i)(j) 650 °C. Reproduced with permission from Ref. [331] (Copyright 2019 Elsevier).

Fig.28 Formation and growth of metal NPs by high power laser irradiation.

Composite	Host matrix	Reinforcement	Size of NPs (min?max (mean))/nm	Loading of NPs (wt.% in excess)	Ion-exchange technique	Application	Ref.
Ag NPs@aluminosilicate glass	Aluminosilicate glass (75.63 wt.% SiO₂, 8.83 wt.% Na₂O, 7.92 wt.% CaO, 4.22 wt.% MgO, 1.81 wt.% SnO₂, 0.74 wt.% Al₂O₃, 0.43 wt.% Fe₂O₃, 0.27 wt.% SO₃, and 0.14 wt.% K₂O)	Ag NPs	2.5?6	?	Staining process: pigment (red ochre); annealing (T < 660 °C for 1 h and 40 min)	Art	[371]
Cu NPs@aluminosilicate glass	Aluminosilicate glass (77.82 wt.% SiO₂, 6.52 wt.% Na₂O, 7.50 wt.% CaO, 4.24 wt.% MgO, 1.88 wt.% SnO₂, 0.76 wt.% Al₂O₃, 0.03 wt.% Fe₂O₃, 0.25 wt.% SO₃, and 1.00 wt.% K₂O)	Cu NPs	25?40	?	Staining process: pigment (red ochre); annealing (T < 660 °C for 1 h and 40 min)	Art	[371]
Au NPs@silica glass	Silica glass	Au NPs	3?10	0.05	Spark plasma sintering: uniaxial pressure (50 MPa), in vacuum at 1020 °C for 3 min	NLO devicesβ_{(720 nm)} = 5.72 × 10^?12 m·W^?1	[372]
GaAs NPs@silica glass	Silica glass	GaAs NPs	2.7	?	Radio frequency sputtering: 13.56 MHz radio frequency sputtering, 4.7 mTorr Ar atmosphere at room temperature, radio frequency power (15 W), sputtering time (30 s)	?	[373]
GaAs NPs@silica glass	Silica glass	GaAs NPs	4.4	?	Radio frequency sputtering: 13.56 MHz radio frequency sputtering, 4.7 mTorr Ar atmosphere at room temperature, radio frequency power (15 W), sputtering time (60 s)
GaAs NPs@silica glass	Silica glass	GaAs NPs	7.7	?	Radio frequency sputtering: 13.56 MHz radio frequency sputtering, 4.7 mTorr Ar atmosphere at room temperature, radio frequency power (15 W), sputtering time (90 s)
Au NPs@silica glass	Silica glass	Au NPs	2.43	?	Radio frequency sputtering: 13.56 MHz radio frequency sputtering, 4.7 mTorr Ar atmosphere at room temperature, radio frequency power (10 W), sputtering time (30 s)
Au NPs@silica glass	Silica glass	Au NPs	3.64	?	Radio frequency sputtering: 13.56 MHz radio frequency sputtering, 4.7 mTorr Ar atmosphere at room temperature, radio frequency power (10 W), sputtering time (60 s)
Au NPs@silica glass	Silica glass	Au NPs	8.09	?	Radio frequency sputtering: 13.56 MHz radio frequency sputtering, 4.7 mTorr Ar atmosphere at room temperature, radio frequency power (10 W), sputtering time (120 s)	?	[373]
Au NPs@silica glass	Silica glass	Au NPs	17.5	?	Radio frequency sputtering: 13.56 MHz radio frequency sputtering, 4.7 mTorr Ar atmosphere at room temperature, radio frequency power (10 W), sputtering time (300 s)
Au NPs@silica glass	Silica glass	Au NPs	47.08	?	Radio frequency sputtering: 13.56 MHz radio frequency sputtering, 4.7 mTorr Ar atmosphere at room temperature, radio frequency power (10 W), sputtering time (600 s)
Cu NPs@silica glass	Silica glass	Cu NPs	14	?	Radio frequency sputtering: 13.56 MHz radio frequency sputtering, 0.003?0.004 mTorr Ar atmosphere at room temperature, radio frequency power, silica target (250 W), radio frequency power, Cu target (25 W), co-sputtering time (105 min)	?	[374]
Cu NPs@silica glass	Silica glass	Cu NPs	12	?	Radio frequency sputtering: 13.56 MHz radio frequency sputtering, 0.003?0.004 mTorr Ar atmosphere at room temperature, radio frequency power, silica target (250 W), radio frequency power, Cu target (40 W), co-sputtering time (90 min)	?	[374]
Ag NPs@mesoporous bioactive glasses	Mesoporous bioactive glass^a)	Ag NPs	(9 ± 4)	?	Spray pyrolysis: dispersion of precursors into droplets, preheating at 400 °C, calcination at 700 °C, annealing 500 °C	Antibacterial activity	[154]
Ag NPs@mesoporous bioactive glasses	Mesoporous bioactive glass^b)	Ag NPs	(7 ± 3)	?	Spray pyrolysis: dispersion of precursors into droplets, preheating at 400 °C, calcination at 700 °C, annealing 500 °C	Antibacterial activity	[154]
Ag NPs@Mesoporous bioactive glasses	Mesoporous bioactive glass^a)	Ag NPs	(8 ± 2)	1.64 mol.%	Spray pyrolysis: dispersion of precursors into droplets, preheating at 400 °C, calcination at 700 °C, annealing 500 °C	Antibacterial activity	[375]
Ag NPs@mesoporous bioactive glasses	Mesoporous bioactive glass^a)	Ag NPs	(8 ± 3)	3.28 mol.%	Spray pyrolysis: dispersion of precursors into droplets, preheating at 400 °C, calcination at 700 °C, annealing 500 °C
Ag NPs@mesoporous bioactive glasses	Mesoporous bioactive glass^a)	Ag NPs	(9 ± 3)	6.56 mol.%	Spray pyrolysis: dispersion of precursors into droplets, preheating at 400 °C, calcination at 700 °C, annealing 500 °C
Au NPs@silica glass	Silica glass	Ag NPs	(50)	?	Chemical vapor deposition: aerosol assisted chemical vapor deposition, Au NPs in toluene, aerosol generation (ultrasonic humidification), N₂ flow rate (1 L·min^?1), glass temperature 450 °C	?	[376]

Tab.6 GNCs prepared by staining process, spark plasma sintering, radio frequency sputtering, spray pyrolysis, and CVD techniques [371–376]

Fig.31 Schematic illustration of the features of a spark plasma sintering apparatus.

Fig.32 Schematic illustration of the radio frequency sputtering process.

Fig.33 TEM images of GaAs NPs embedded in silica glass prepared by radio frequency sputtering for (a) 30 s, (b) 60 s, (c) 90 s, (d) 120 s, and (e) 240 s. Reproduced with permission from Ref. [373] (Copyright 1997 AIP Publishing).

Fig.34 TEM images of Au NPs embedded in silica glass prepared by radio frequency sputtering for (a) 30 s, (b) 60 s, (c) 120 s, (d) 300 s, and (e) 600 s. Reproduced with permission from Ref. [373] (Copyright 1997 AIP Publishing).

Fig.35 Cross-sectional TEM images of the GNC made of Au₄₇Cu₅₃ alloy embedded within a glass matrix: (a) low-magnification bright-field image (the inset is the size-histogram); (b) high-resolution image of an Au₄₇Cu₅₃ alloy embedded within a glass matrix. Reproduced with permission from Ref. [397] (Copyright 2007 Elsevier).

Fig.36 Schematic illustration of the steps to prepare GNCs by spray pyrolysis.

Fig.37 Schematic illustration of the AACVD system.

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